4104
M. Adeel et al. / Tetrahedron 65 (2009) 4099–4105
Me3SiOTf (0.08 mL, 0.45 mmol), 6d was isolated as a yellow solid
(s) cmꢁ1; GC–MS (EI, 70 eV) m/z (%): 488 (Mþ, [2ꢂ81Br], 13), 486
(Mþ, [81Br79Br], 27), 484 (Mþ, [2ꢂ79Br], 13), 442 (23), 440 (47), 399
(29), 371 (34), 278 (100), 147 (32), 120 (40). HRMS (EI) calcd for
C18H14Br2O6 [Mþ, 2ꢂ79Br]: 483.91516, found: 483.915113.
(260 mg, 47%), mp¼60–63 ꢀC; 1H NMR (250 MHz, CDCl3):
¼1.22–
d
1.32 (m, 9H, 3CH3), 2.88 (m,1H, CH), 4.07 (s, 2H, CH2), 4.25 (q, 2H,
J¼7.2 Hz, OCH2), 7.04 (d, 1H, J¼8.6 Hz, ArH), 7.14 (d, 1H, J¼8.6 Hz,
ArH), 7.40–7.48 (m, 2H, ArH), 7.90 (dd,1H, J¼2.0, 8.8 Hz, ArH), 8.17 (d,
1H, J¼2.1 Hz, ArH), 11.59 (s, 1H, OH), 12.30 (s, 1H, OH); 13C NMR
3.3.8. Ethyl 3-(5-(5-chloro-2-hydroxybenzoyl)-2-hydroxyphenyl)-
3-oxopropanoate (6h)
Starting with 6,8-dibromo-3-formylchromone 4h (312 mg,
1.5 mmol), 1,3,5-tris(silyl enol ether) 3 (641 mg, 1.65 mmol), and
Me3SiOTf (0.08 mL, 0.45 mmol), 6h was isolated as a reddish brown
solid (203 mg, 37%), mp¼98–99 ꢀC; 1H NMR (250 MHz, CDCl3):
(75.46 MHz, CDCl3):
61.9 (OCH2), 118.3 (C), 118.4 (CH), 118.5 (C), 118.7 (CH), 129.2 (C),
129.9, 132.9, 134.9, 137.8 (CH), 139.2 (C), 161.1, 165.6 (COH), 166.3,
d
¼14.1, 23.9, 24.0 (CH3), 33.1 (CH), 45.7 (CH2),
198.5,198.5 (C]O); IR (neat):
n
¼3058 (w), 2956 (m), 2924 (m),1744
(s),1681 (w),1653 (m),1628 (s),1583 (s),1480 (s),1343 (m),1207 (s),
1181 (s), 832 (s) cmꢁ1; GC–MS (EI, 70 eV) m/z (%): 370 (Mþ, 77), 324
(53), 309 (78), 283 (17), 267 (23), 162 (46), 147 (100), 44 (37); HRMS
(EI) calcd for C21H22O6 [Mþ]: 370.14109, found: 370.140462.
d
¼1.30 (t, 3H, J¼7.1 Hz, CH3), 4.07 (s, 2H, CH2), 4.25 (q, 2H, J¼7.1 Hz,
OCH2), 7.07 (d, 1H, J¼9.0 Hz, ArH), 7.16 (d, 1H, J¼8.7 Hz, ArH), 7.48–
7.52 (m, 1H, ArH), 7.56 (d, 1H, J¼2.5 Hz, ArH), 7.90 (dd, 1H, J¼2.0,
8.7 Hz, ArH), 8.16 (d, 1H, J¼1.95 Hz, ArH), 11.63 (s, 1H, OH), 12.33 (s,
3.3.5. Ethyl 3-(2-hydroxy-5-(2-hydroxy-5-nitrobenzoyl)phenyl)-
3-oxopropanoate (6e)
Starting with 6-nitro-3-formylchromone 4e (328 mg, 1.5 mmol),
1,3,5-tris(silyl enol ether) 3 (641 mg, 1.65 mmol), and Me3SiOTf
(0.08 mL, 0.45 mmol), 6e was isolated as a yellow solid (160 mg,
1H, OH); 13C NMR (75.46 MHz, CDCl3):
d¼14.1 (CH3), 45.7 (CH2), 62.0
(OCH2), 118.6 (C), 119.1 (CH), 119.4 (C), 120.3 (CH), 123.6, 128.3 (C),
131.5, 133.0, 136.2, 137.6 (CH), 161.4, 164.5 (COH), 166.3, 197.5, 198.4
(C]O); IR (neat):
n
¼3074 (w), 2978 (m), 2932 (w),1728 (m),1668 (s),
1626 (s), 1587 (s), 1459 (s), 1274 (s), 1173 (s), 1095 (s), 834 (m) cmꢁ1
;
29%), mp¼130–133 ꢀC. 1H NMR (300 MHz, CDCl3):
d
¼1.19 (t, 3H,
GC–MS (EI, 70 eV): m/z (%): 364 (Mþ, 37Cl, 20), 362 (Mþ, 35Cl, 47), 316
(100), 301 (25), 273 (34), 245 (15), 207 (14), 155 (35), 44 (29); HRMS
(EI) calcd for C18H15O6Cl [Mþ, 35Cl]: 362.05517, found: 362.054802.
J¼7.1 Hz, CH3), 3.96 (s, 2H, CH2), 4.25 (q, 2H, J¼7.1 Hz, OCH2), 7.10
(m, 2H, ArH), 7.36 (m, 2H, ArH), 7.84 (dd,1H, J¼2.1, 8.7 Hz, ArH), 8.14
(d, J¼2.0 Hz, 1H, ArH), 8.30 (m, 1H, ArH), 12.30 (br, 2H, OH); 13C
NMR (75.47 MHz, CDCl3):
d
¼14.0 (CH3), 45.9 (CH2), 62.1 (OCH2),
3.3.9. Ethyl 3-(5-(3,5-dichloro-2-hydroxybenzoyl)-2-hydroxy-
phenyl)-3-oxopropanoate (6i)
117.6, 118.7 (C), 119.5, 119.7, 128.8, 129.4, 130.8, 133.5 (CH), 137.5,
139.5 (C), 166.1, 166.5 (COH), 167.7, 197.3, 198.3 (C]O); IR (neat):
Starting with 6,8-dichloro-3-formylchromone 4i (240 mg,
1 mmol), 1,3,5-tris(silyl enol ether) 3 (430 mg, 1.1 mmol), and
Me3SiOTf (0.05 mL, 0.3 mmol), 6i was isolated as a light yellow
solid (230 mg, 59%), mp¼124–125 ꢀC. 1H NMR (250 MHz, CDCl3):
n
¼3088 (w), 2969 (w), 2849 (w), 1726 (s), 1628 (s), 1593 (s), 1519
(m), 1470 (s), 1338 (s), 1209 (s), 742 (s) cmꢁ1; GC–MS (EI, 70 eV) m/z
(%): 373 (Mþ, 37), 327 (100), 310 (23), 286 (64), 258 (40), 166 (40),
147 (25), 120 (60); HRMS (EI) calcd for C18H15NO8 [Mþ]: 373.07922,
found: 373.078728.
d
¼1.21 (t, 3H, J¼6.9 Hz, CH3), 3.97 (s, 2H, CH2), 4.14 (q, 2H, J¼7.1 Hz,
OCH2), 7.06 (d, 1H, J¼8.7 Hz, ArH), 7.58 (d, 1H, J¼2.3 Hz, ArH), 7.78–
7.84 (m, 2H, ArH), 8.07 (d, J¼2.0 Hz,1H, ArH),12.13 (s,1H, OH),12.27
3.3.6. Ethyl 3-(5-(5-bromo-2-hydroxybenzoyl)-2-hydroxyphenyl)-
3-oxopropanoate (6f)
Starting with 6-bromo-3-formylchromone 4f (379 mg,
1.5 mmol), 1,3,5-tris(silyl enol ether) 3 (641 mg, 1.65 mmol), and
Me3SiOTf (0.08 mL, 0.45 mmol), 6f was isolated as a yellow solid
(s, 1H, OH); 13C NMR (75.46 MHz, CDCl3):
62.1 (OCH2), 110.4, 113.5, 118.7 (C), 119.2 (CH), 120.6, 128.3 (C), 133.3,
133.8, 137.6, 141.3 (CH), 158.4, 166.2 (COH), 166.3, 197.0, 198.4
d
¼14.0 (CH3), 45.7 (CH2),
(C]O); IR (neat):
n
¼3068 (w), 2976 (w), 2938 (m), 2869 (m), 1735
(s), 1656 (w), 1628 (s), 1588 (s), 1576 (s), 1214 (s), 1161 (s), 771
(190 mg, 31%), mp¼117–120 ꢀC. 1H NMR (250 MHz, CDCl3):
d
¼1.21
(s) cmꢁ1; MS (EI, 70 eV) m/z (%): 400 (Mþ, [2ꢂ37Cl], 3), 398 (Mþ,
(t, 3H, J¼6.9 Hz, CH3), 2.68 (s, 2H, CH2), 4.23 (q, 2H, J¼7.1 Hz, OCH2),
6.91 (d, 1H, J¼8.85 ArH), 7.06 (d, 1H, J¼8.75 Hz, ArH), 7.51 (m, 1H,
ArH), 7.79 (d, 1H, J¼1.75 Hz, ArH), 7.83 (d, J¼1.75 Hz, 1H, ArH), 8.06
(d, J¼1.8 Hz, 1H, ArH), 11.56 (s, 1H, OH), 12.24 (s, 1H, OH); 13C NMR
[
37Cl35Cl], 22), 396 (Mþ, [2ꢂ35Cl], 34), 353 (6), 350 (51), 309 (40),
190 (67), 188 (100). HRMS (EI) calcd for C18H14Cl2O6 [Mþ, 2ꢂ35Cl]:
396.01620, found: 396.015918.
(75.46 MHz, CDCl3):
d¼14.0 (CH3), 45.7 (CH2), 62.0 (OCH2), 110.4,
3.3.10. Ethyl 3-(5-(5-fluoro-2-hydroxybenzoyl)-2-hydroxy-
phenyl)-3-oxopropanoate (6j)
118.6 (C), 119.1 (CH), 120.1 (C), 120.6 (CH), 128.3 (C), 133.0, 134.5,
137.3, 138.9 (CH), 161.8, 166.0 (COH), 166.3, 197.2, 198.5 (C]O); IR
Starting with 6,8-dibromo-3-formylchromone 4j (288 mg,
1.5 mmol), 1,3,5-tris(silyl enol ether) 3 (641 mg, 1.65 mmol), and
Me3SiOTf (0.08 mL, 0.45 mmol), 6j was isolated as a light yellow
solid (179 mg, 34%), mp¼72–74 ꢀC; 1H NMR (250 MHz, CDCl3):
(neat):
n
¼3073 (w), 3002 (w), 2966 (m), 1728 (s), 1680 (s), 1643 (s),
1626 (m), 1447 (s), 1462 (s), 1422 (s), 786 (s) cmꢁ1; GC–MS (EI,
70 eV) m/z (%): 408 (Mþ, 81Br, 47), 406 (Mþ, 79Br, 47), 362 (78), 360
(75), 291 (28), 200 (100),147 (30),120 (41), 92 (14); HRMS (EI) calcd
for C18H15BrO6 [Mþ, 79Br]: 406.00465, found: 406.004404.
d
¼1.22 (t, 3H, J¼7.1 Hz, CH3), 3.97 (s, 2H, CH2), 4.22 (q, 2H, J¼7.1 Hz,
OCH2), 6.96–6.99 (m, 1H, ArH), 7.08 (d, 1H, J¼8.75 Hz, ArH), 7.20 (m,
1H, ArH), 7.81 (d, 1H, J¼2.0 Hz, ArH), 7.85 (d, 1H, J¼2.1 Hz, ArH),
8.06 (d, 1H, J¼2.0 Hz, ArH), 11.39 (s, 1H, OH), 12.23 (s, 1H, OH); 13C
3.3.7. Ethyl 3-(5-(3,5-dibromo-2-hydroxybenzoyl)-2-hydroxy-
phenyl)-3-oxopropanoate (6g)
NMR (75.46 MHz, CDCl3):
118.6 (C), 119.1 (CH), 119.4 (C), 120.3 (CH), 123.6, 128.3 (C), 131.5,
133.0, 136.2, 137.6 (CH), 161.4, 164.5 (COH), 166.3, 197.5, 198.4
d
¼14.1 (CH3), 45.7 (CH2), 62.0 (OCH2),
Starting with 6,8-dibromo-3-formylchromone 4g (331 mg,
1.0 mmol), 1,3,5-tris(silyl enol ether) 3 (427 mg, 1.1 mmol), and
Me3SiOTf (0.05 mL, 0.3 mmol), 6g was isolated as a light brown
solid (159 mg, 33%), mp¼101–103 ꢀC; 1H NMR (250 MHz, CDCl3):
(C]O); IR (neat):
n
¼3069 (w), 2998 (w), 2974 (w),1726 (s), 1655 (s),
1634 (s), 1622 (m), 1470 (s), 1598 (s), 1469 (s), 987 (s) cmꢁ1; GC–MS
(EI, 70 eV) m/z (%): 346 (Mþ, 50), 326 (18), 300 (44), 259 (50), 231
(70), 139 (100), 120 (31), HRMS (EI) calcd for C18H15FO6 [Mþ]:
346.08472, found: 346.084658.
d
¼1.21 (t, 3H, J¼6.9 Hz, CH3), 3.97 (s, 2H, CH2), 4.14 (q, 2H, J¼7.1 Hz,
OCH2), 7.06 (d, 1H, J¼8.7 Hz, ArH), 7.58 (d, 1H, J¼2.3 Hz, ArH), 7.78–
7.84 (m, 2H, ArH), 8.07 (d, J¼2.0 Hz,1H, ArH),12.13 (s,1H, OH),12.27
(s, 1H, OH); 13C NMR (75.46 MHz, CDCl3):
d
¼14.0 (CH3), 45.7 (CH2),
62.1 (OCH2), 110.4, 113.5, 118.7 (C), 119.2 (CH), 120.6, 128.3 (C), 133.3,
133.8, 137.6, 141.3 (CH), 158.4, 166.2 (COH), 166.3, 197.0, 198.4
Acknowledgements
(C]O); IR (neat):
(s), 1694 (w), 1651 (s), 1626 (s), 1583 (s), 1214 (s), 1159 (s), 771
n
¼3067 (w), 3002 (w), 2974 (m), 2919 (m), 1735
Financial support by the State of Mecklenburg-Vorpommern is
gratefully acknowledged.