1514
Russ.Chem.Bull., Int.Ed., Vol. 57, No. 7, July, 2008
Traven et al.
m/z (Irel (%)): 426 (85). Found (%): C, 73.68; H, 5.43; N, 6.39.
C26H22N2O4. Calculated (%): C, 73.23; H, 5.20; N, 6.57.
4ꢀHydroxyꢀ3ꢀ[1,5ꢀdi(4ꢀmethoxyphenyl)ꢀ4,5ꢀdihydroꢀ1Hꢀ
pyrazolꢀ3ꢀyl]coumarin (4d). Yield 79%, m.p. 199—201 °C. 1H NMR
(DMSOꢀd6), δ: 3.37 (dd, 1 H, H(9), J = 18.9 Hz, J = 9.7 Hz);
3.68, 3.72 (both s, 3 H each, OCH3); 4.13 (dd, 1 H, H(9), J = 18.9 Hz,
J = 11.7 Hz); 5.21 (dd, 1 H, H(10), J = 9.7 Hz, J = 11.78 Hz); 6.86
(m, 6 H, H(11), H(12), H(14), H(15), H(17), H(19)); 7.38 (m, 4 H,
H(6), H(8), H(16), H(20)); 7.69 (m, 1 H, H(7)); 7.98 (d, 1 H,
H(5), J = 8.2 Hz); 13.86 (s, 1 H, OH). MS, m/z (Irel (%)): 442 (95).
Found (%): C, 71.01; H, 5.13; N, 6.18. C26H22N2O5. Calculatꢀ
ed (%): C, 70.58; H, 5.01; N, 6.33.
4ꢀHydroxyꢀ3ꢀ[5ꢀ(4ꢀmethoxyphenyl)ꢀ1ꢀ(4ꢀnitrophenyl)ꢀ4,5ꢀ
dihydroꢀ1Hꢀpyrazolꢀ3ꢀyl]coumarin (4e). Yield 72%, m.p. 261—263 °C.
1H NMR (DMSOꢀd6), δ: 3.43 (dd, 1 H, H(9), J = 19.4 Hz,
J = 6.1 Hz); 3.63 (s, 3 H, OCH3); 4.18 (dd, 1 H, H(9), J = 19.4 Hz,
J = 11.7 Hz); 5.15 (dd, 1 H, H(10), J = 6.1 Hz, J = 11.7 Hz);
6.94—7.26 (m, 6 H, H(11), H(12), H(14), H(15), H(16), H(20));
7.48 (m, 2 H, H(6), H(8)); 7.71 (m, 1 H, H(7)); 8.08—8.14
(m, 3 H, H(5), H(17), H(19)); 13.82 (s, 1 H, OH). MS, m/z
(Irel (%)): 457 (90). Found (%): C, 65.32; H, 4.29; N, 9.31.
C25H19N3O6. Calculated (%): C, 65.64; H, 4.19; N, 9.19.
3ꢀ[5ꢀ(2,4ꢀDimethoxyphenyl)ꢀ1ꢀphenylꢀ4,5ꢀdihydroꢀ1Hꢀpyrꢀ
azolꢀ3ꢀyl]ꢀ4ꢀhydroxycoumarin (4f). Yield 61%, m.p. 202—203 °C
(cf. Ref. 15: m.p. 218 °C). 1H NMR (DMSOꢀd6), δ: 3.30 (dd, 1 H,
H(9), J = 18.8 Hz, J = 6.7 Hz); 3.75, 3.90 (both s, 3 H each,
OCH3); 4.15 (dd, 1 H, H(9), J = 18.8 Hz, J = 12.4 Hz); 5.40
(dd, 1 H, H(10), J = 6.7 Hz, J = 12.4 Hz); 6.30 (d, 1 H, H(12),
J = 7.8 Hz); 6.52 (s, 1 H, H(14)); 6.80 (m, 3 H, H(16), H(17),
H(19)); 6.90 (d, 1 H, H(11), J = 7.8 Hz); 7.16 (m, 2 H, H(16),
H(20)); 7.30 (m, 2 H, H(6), H(8)); 7.60 (m, 1 H, H(7)); 7.94 (d, 1 H,
H(5), J = 6.8 Hz); 13.95 (s, 1 H, OH). MS, m/z (Irel (%)): 442 (90).
Found (%): C, 70.52; H, 5.06; N, 6.28. C26H22N2O5. Calculatꢀ
ed (%): C, 70.58; H, 5.01; N, 6.33.
3ꢀ[5ꢀ(2,4ꢀDimethoxyphenyl)ꢀ1ꢀ(4ꢀfluorophenyl)ꢀ4,5ꢀdihydroꢀ
1Hꢀpyrazolꢀ3ꢀyl]ꢀ4ꢀhydroxycoumarin (4g). Yield 74%, m.p.
>350 °C. 1H NMR (DMSOꢀd6), δ: 3.63 (dd, 1 H, H(9), J = 18.4 Hz,
J = 12.4 Hz); 3.74, 3.85 (both s, 3 H each, OCH3); 4.07 (dd, 1 H,
H(9), J = 18.4 Hz, J = 6.4 Hz); 5.45 (dd, 1 H, H(10), J = 6.4 Hz,
J = 12.4 Hz); 6.46 (d, 1 H, H(12), J = 8.3 Hz); 6.63 (s, 1 H, H(14));
6.73—7.11 (m, 5 H, H(11), H(16), H(17), H(19), H(20)); 7.44
(m, 2 H, H(6), H(8)); 7.71 (m, 1 H, H(7)); 8.00 (d, 1 H, H(5),
J = 7.4 Hz); 14.18 (s, 1 H, OH). MS, m/z (Irel (%)): 460 (73).
Found (%): C, 67.61; H, 4.73; N, 6.19. C26H21FN2O5. Calculatꢀ
ed (%): C, 67.82; H, 4.60; N, 6.08.
H(10), J = 5.6 Hz, J = 11.8 Hz); 6.36 (d, 1 H, H(12), J = 8.2 Hz);
6.50 (s, 1 H, H(14)); 6.84 (d, 2 H, H(16), H(20), J = 9.0 Hz);
7.35—7.44 (m, 3 H, H(6), H(8), H(11)); 7.57 (m, 1 H, H(7));
8.06—8.15 (m, 3 H, H(5), H(17), H(19)); 13.60 (s, 1 H, OH).
MS, m/z (Irel (%)): 487 (80). Found (%): C, 64.24; H, 4.18;
N, 8.53. C26H21N3O7. Calculated (%): C, 64.06; H, 4.34; N, 8.62.
3ꢀ{5ꢀ[4ꢀ(N,NꢀDimethylamino)phenyl]ꢀ1ꢀphenylꢀ4,5ꢀdihydroꢀ
1Hꢀpyrazolꢀ3ꢀyl}ꢀ4ꢀhydroxycoumarin (4j). Yield 54%, m.p.
229—231 °C. 1H NMR (DMSOꢀd6), δ: 2.93 (s, 6 H, (CH3)2); 3.57
(dd, 1 H, H(9), Jgem = 18.96 Hz, Jvic = 6.28 Hz); 4.19 (dd, 1 H,
H(9), Jgem = 18.96 Hz, Jvic = 12.30 Hz); 5.12 (dd, 1 H, H(10),
Jcis = 6.28 Hz, Jtrans = 12.30 Hz); 6.68 (d, 2 H, H(12), H(14),
J = 8.41 Hz); 6.85 (m, 1 H, H(18)); 6.96 (m, 2 H, H(17), H(19));
7.13—7.25 (m, 4 H, H(11), H(15), H(16), H(20)); 7.30 (m, 2 H,
H(6), H(8)); 7.56 (m, 1 H, H(7)); 8.02 (d, 1 H, H(5), J = 7.32 Hz);
14.11 (s, 1 H, OH). MS, m/z (Irel (%)): 425 (100). Found (%):
C, 73.38; H, 5.48; N, 9.82. C26H23N3O3. Calculated (%): C, 73.40;
H, 5.45; N, 9.88.
3ꢀ{5ꢀ[4ꢀ(N,NꢀDimethylamino)phenyl]ꢀ1ꢀ(4ꢀfluorophenyl)ꢀ4,5ꢀ
dihydroꢀ1Hꢀpyrazolꢀ3ꢀyl}ꢀ4ꢀhydroxycoumarin (4k). Yield 74%,
m.p. >350 °C. 1H NMR (DMSOꢀd6), δ: 2.54 (s, 6 H, 2 CH3); 3.03
(dd, 1 H, H(9), J = 18.9 Hz, J = 8.7 Hz); 4.05 (dd, 1 H, H(9),
J = 18.9 Hz, J = 12.3 Hz); 5.23 (dd, 1 H, H(10), J = 8.7 Hz,
J = 12.3 Hz); 6.68 (d, 2 H, H(12), H(14), J = 8.3 Hz); 6.84—7.06
(m, 6 H, H(11), H(15), H(16), H(17), H(19), H(20)); 7.42 (m, 2 H,
H(6), H(8)); 7.69 (m, 1 H, H(7)); 7,98 (d, 1 H, H(5), J = 6.4 Hz);
14.47 (s, 1 H, OH). MS, m/z (Irel (%)): 443 (65). Found (%):
C, 70.21; H, 5.09; N, 9.31. C26H22FN3O3. Calculated (%):
C, 70.42; H, 5.00; N, 9.48.
3ꢀ{5ꢀ[4ꢀ(N,NꢀDimethylamino)phenyl]ꢀ1ꢀ(4ꢀmethoxyphenyl)ꢀ
4,5ꢀdihydroꢀ1Hꢀpyrazolꢀ3ꢀyl}ꢀ4ꢀhydroxycoumarin (4l). Yield
1
77%, m.p. 175—177 °C. H NMR (DMSOꢀd6), δ: 2.91 (s, 6 H,
2 CH3); 3.35 (dd, 1 H, H(9), J = 18.9 Hz, J = 9.2 Hz); 3.62 (s, 3 H,
OCH3); 4.12 (dd, 1 H, H(9), J = 18.9 Hz, J = 11.7 Hz); 5.11
(dd, 1 H, H(10), J = 9.2 Hz, J = 11.7 Hz); 6.63—6.92 (m, 6 H,
H(11), H(12), H(14), H(15), H(17), H(19)); 7.17 (d, 2 H, H(16),
H(20), J = 9.3 Hz); 7.38 (m, 2 H, H(6), H(8)); 7.65 (m, 1 H,
H(7)); 7.96 (d, 1 H, H(5), J = 7.3 Hz); 14.06 (s, 1 H, OH). MS, m/z
(Irel (%)): 455 (65). Found (%): C, 71.40; H, 5.39; N, 9.12.
C27H25N3O4. Calculated (%): C, 71.19; H, 5.53; N, 9.22.
3ꢀ[5ꢀ(Benzothiazolꢀ2ꢀyl)ꢀ1ꢀ(4ꢀmethoxyphenyl)ꢀ4,5ꢀdihydroꢀ
1Hꢀpyrazolꢀ3ꢀyl]ꢀ4ꢀhydroxycoumarin (4m). Yield 79%, m.p.
241—243 °C. 1H NMR (DMSOꢀd6), δ: 3.47 (dd, 1 H, H(9),
J = 18.8 Hz, J = 12.4 Hz); 3.69 (s, 3 H, OCH3); 4.22 (dd, 1 H,
H(9), J = 18.8 Hz, J = 6.7 Hz); 5.69 (dd, 1 H, H(10), J = 6.7 Hz,
J = 12.4 Hz); 6.88 (d, 2 H, H(12), H(14), J = 8.3 Hz); 7.13
(m, 1 H, H(17)); 7.31 (m, 3 H, H(11), H(15), H(19)); 7.46 (m, 3 H,
H(6), H(8), H(18)); 7.76 (m, 1 H, H(7)); 7.82 (d, 1 H, H(16),
J = 7.8 Hz); 8.02 (d, 1 H, H(5), J = 7.8 Hz). MS, m/z (Irel (%)): 469
(70). Found (%): C, 66.21; H, 4.14; N, 8.69. C26H19N3O4S.
Calculated (%): C, 66.52; H, 4.05; N, 8.96.
3ꢀ[5ꢀ(Benzothiazolꢀ2ꢀyl)ꢀ1ꢀ(2,4ꢀdimethoxyphenyl)ꢀ4,5ꢀdihyꢀ
droꢀ1Hꢀpyrazolꢀ3ꢀyl]ꢀ4ꢀhydroxycoumarin (4n). Yield 74%, m.p.
225—227 °C. 1H NMR (DMSOꢀd6), δ: 3.39 (dd, 1 H, H(9),
J = 18.9 Hz, J = 12.4 Hz); 3.68, 3.82 (both s, 3 H each, OCH3);
4.11 (dd, 1 H, H(9), J = 18.9 Hz, J = 6.3 Hz); 5.71 (dd, 1 H, H(10),
J = 6.3 Hz, J = 12.4 Hz); 6.45 (d, 1 H, H(12), J = 8.2 Hz); 6.64
(s, 1 H, H(14)); 6.97 (d, 1 H, H(11), J = 8.2 Hz); 7.12 (m, 1 H,
H(17)); 7.25 (m, 1 H, H(18)); 7.43 (m, 3 H, H(6), H(8), H(19));
7.67 (m, 1 H, H(7)); 7.84 (d, 1 H, H(16), J = 7.9); 8.01 (d, 1 H,
H(5), J = 8.2 Hz). MS, m/z (Irel (%)): 487 (85). Found (%):
3ꢀ[5ꢀ(2,4ꢀDimethoxyphenyl)ꢀ1ꢀ(4ꢀtolyl)ꢀ4,5ꢀdihydroꢀ1Hꢀ
pyrazolꢀ3ꢀyl]ꢀ4ꢀhydroxycoumarin (4h). Yield 75%, m.p. >350 °C.
1H NMR (DMSOꢀd6), δ: 2.17 (s, 3 H, CH3); 3.39 (dd, 1 H, H(9),
J = 18.9 Hz, J = 7.7 Hz); 3.71, 3.78 (both s, 3 H each, OCH3);
4.09 (dd, 1 H, H(9), J = 18.9 Hz, J = 12.3 Hz); 5.46 (dd, 1 H,
H(10), J = 7.7 Hz, J = 12.3 Hz); 6.41 (d, 1 H, H(12), J = 8.5 Hz);
6.65 (s, 1 H, H(14)); 6.77 (d, 1 H, H(11), J = 8.5 Hz); 7.02—7.14
(m, 4 H, H(16), H(17), H(19), H(20)); 7.46 (m, 2 H, H(6), H(8));
7.71 (m, 1 H, H(7)); 8.01 (d, 1 H, H(5), J = 7.9 Hz); 14.27 (s, 1 H,
OH). MS, m/z (Irel (%)): 456 (75). Found (%): C, 71.22; H, 5.49;
N, 6.21. C27H24N2O5. Calculated (%): C, 71.04; H, 5.30; N, 6.14.
3ꢀ[5ꢀ(2,4ꢀDimethoxyphenyl)ꢀ1ꢀ(4ꢀnitrophenyl)ꢀ4,5ꢀdihydroꢀ
1Hꢀpyrazolꢀ3ꢀyl]ꢀ4ꢀhydroxycoumarin (4i). Yield 71%, m.p.
225—227 °C. 1H NMR (DMSOꢀd6), δ: 3.61 (dd, 1 H, H(9),
J = 19.48 Hz, J = 5.64 Hz); 3.75, 3.88 (both s, 3 H each, OCH3);
4.20 (dd, 1 H, H(9), J = 19.4 Hz, J = 11.8 Hz); 4.58 (dd, 1 H,