J. Zhang et al. / European Journal of Medicinal Chemistry 46 (2011) 5711e5716
5715
i
Yellow solid. Anal. Calc. for C18H14Cl2N2Pd: C, 49.63; H, 3.24;
N, 6.43. Found: C, 49.88; H, 3.40; N, 6.53.
3H, CH3), 1.02 (t, J ¼ 7.4 Hz, 3H, CH3). ESI-MS: 668.1[M -
2H2O þ Na]þ. Anal. Calc. for C31H33N3O6PdS(681.1): C, 54.59; H,
4.88; N, 6.16. Found: C, 54.77; H, 4.21; N, 6.24.
ii Yellow solid. Anal. Calc. for C4H12Cl2N2Pd: C, 18.10; H, 4.56; N,
10.55. Found: C, 18.44; H, 4.12; N, 10.22.
4.3.5. Synthesis of [Pd(bqu)(TsserNO)] (5)
The synthesis of 5 was carried out in an identical manner to 1
starting from [Pd(bqu)Cl2] (15 mg, 0.035 mmol) and TsserH2
(17 mg, 0.070 mmol). Yellow solid. IR (KBr, cmꢀ1): 1665, 1369, 569,
4.3.1. Synthesis of [Pd(bqu)(TsalaNO)] (1)
[Pd(bqu)Cl2] (15 mg, 0.035 mmol) was added to 3 ml CH3OH/
H2O (volume 1:1) solution which was adjusted to pH ¼ 8e9 by
NaOH solution. TsalaH2 (17 mg, 0.070 mmol) was added to the
mixture and then the mixture was stirred at 50 ꢁC for 5 h. The
yellow precipitate was filtered, washed 5 times with 1:1 mixture of
water-ethanol, and dried under vacuum condition. Yellow solid. IR
(KBr, cmꢀ1): 1656, 1366, 570, 403, 469. 1H NMR (600 MHz, DMSO,
403, 491. 1H NMR (600 MHz, DMSO, 25 ꢁC):
d
9.49 (d, J ¼ 8.8 Hz, 1H,
ArH), 9.06 (d, J ¼ 8.7 Hz, 1H, ArH), 8.98 (d, J ¼ 8.6 Hz, 1H, ArH), 8.91
(d, J ¼ 8.7 Hz, 1H, ArH), 8.82 (d, J ¼ 8.8 Hz, 1H, ArH), 8.64 (d,
J ¼ 8.8 Hz, 1H, ArH), 8.22 (d, J ¼ 8.1 Hz, 1H, ArH), 8.16 (d, J ¼ 8.0 Hz,
1H, ArH), 8.00e7.89 (m, 2H, ArH), 7.84 (dd, J ¼ 13.7, 6.7 Hz, 2H, ArH),
7.48 (d, J ¼ 8.1 Hz, 2H, ArH), 7.09 (d, J ¼ 8.0 Hz, 2H, ArH), 5.56 (t,
J ¼ 5.1 Hz, 1H, OH), 4.11 (dd, J ¼ 10.5, 3.7 Hz, 1H, CH2), 3.86 (dd,
J ¼ 10.6, 3.7 Hz, 1H, CH2), 3.43 (t, J ¼ 3.7 Hz, 1H, CH), 2.23 (s, 3H,
CH3). ESI-MS: 642.1[M þ Na]þ. Anal. Calc. for C28H23N3O5PdS
(619.0): C, 54.24; H, 3.74; N, 6.78. Found: C, 54.42; H, 3.65; N, 6.42.
25 ꢁC):
d
9.22 (d, J ¼ 8.8 Hz, 1H, ArH), 9.09 (d, J ¼ 8.6 Hz, 1H, ArH),
9.01 (d, J ¼ 8.6 Hz, 1H, ArH), 8.94 (d, J ¼ 8.8 Hz, 1H, ArH), 8.85 (d,
J ¼ 8.7 Hz, 1H, ArH), 8.59 (d, J ¼ 8.8 Hz, 1H, ArH), 8.25 (d, J ¼ 8.0 Hz,
1H, ArH), 8.19 (d, J ¼ 8.0 Hz, 1H, ArH), 8.02 (t, J ¼ 7.7 Hz, 1H, ArH),
7.97 (t, J ¼ 7.8 Hz, 1H, ArH), 7.86 (dd, J ¼ 14.1, 7.0 Hz, 2H, ArH), 7.49
(d, J ¼ 8.2 Hz, 2H, ArH), 7.12 (d, J ¼ 8.0 Hz, 2H, ArH), 3.44e3.40 (m,
1H, CH), 2.25 (s, 3H, CH3), 1.80 (d, J ¼ 7.1 Hz, 3H, CH3). ESI-MS: 626.0
[M þ Na]þ. Anal. Calc. for C28H23N3O4PdS(603.0): C, 55.68; H, 3.84;
N, 6.96. Found: C, 55.66; H, 3.65; N, 7.28.
4.3.6. Synthesis of [Pd(bqu)(TspheNO)] (6)
The synthesis of 6 was carried out in an identical manner to 1
starting from [Pd(bqu)Cl2] (15 mg, 0.035 mmol) and TspheH2
(22 mg, 0.070 mmol). Yellow solid. IR (KBr, cmꢀ1): 1665, 1379, 577,
401, 494. 1H NMR (600 MHz, DMSO, 25 ꢁC):
d
9.07 (d, J ¼ 8.6 Hz, 1H,
4.3.2. Synthesis of [Pd(bqu)(TsvalNO)] (2)
ArH), 9.01 (d, J ¼ 8.8 Hz, 1H, ArH), 8.97 (d, J ¼ 8.6 Hz, 1H, ArH), 8.91
(d, J ¼ 8.8 Hz, 1H, ArH), 8.81 (d, J ¼ 8.8 Hz, 1H, ArH), 8.50 (d,
J ¼ 8.8 Hz, 1H, ArH), 8.24 (d, J ¼ 8.1 Hz, 1H, ArH), 8.13 (d, J ¼ 7.9 Hz,
1H, ArH), 7.99 (t, J ¼ 7.3 Hz, 1H, ArH), 7.87 (t, J ¼ 7.1 Hz, 1H, ArH),
7.79 (t, J ¼ 7.3 Hz, 1H, ArH), 7.50 (t, J ¼ 7.3 Hz, 1H, ArH), 7.36 (d,
J ¼ 7.2 Hz, 2H, ArH), 7.30 (t, J ¼ 7.3 Hz, 2H, ArH), 7.26 (d, J ¼ 7.9 Hz,
3H, ArH), 7.02 (d, J ¼ 8.0 Hz, 2H, ArH), 3.79e3.71 (m, 2H, CH2),
3.28e3.22 (m, 1H, CH), 2.27 (s, 3H, CH3). ESI-MS: 679.1 [M þ H]þ.
Anal. Calc. for C34H27N3O4PdS(678.1): C, 60.05; H, 4.00; N, 6.18.
Found: C, 60.00; H, 3.87; N, 6.50.
The synthesis of 2 was carried out in an identical manner to 1
starting from [Pd(bqu)Cl2] (15 mg, 0.035 mmol) and TsvalH2
(19 mg, 0.070 mmol). Yellow solid. IR (KBr, cmꢀ1): 1641, 1360, 582,
406, 497. 1H NMR (600 MHz, DMSO, 25 ꢁC):
d
9.38 (d, J ¼ 8.8 Hz, 1H,
ArH), 9.06 (d, J ¼ 8.7 Hz, 1H, ArH), 9.01 (d, J ¼ 8.6 Hz, 1H, ArH), 8.91
(d, J ¼ 8.8 Hz, 1H, ArH), 8.83 (d, J ¼ 8.8 Hz, 1H, ArH), 8.52 (d,
J ¼ 8.8 Hz,1H, ArH), 8.24e8.16 (m, 2H, ArH), 8.00e7.91 (m, 2H, ArH),
7.85 (dt, J ¼ 14.6, 7.3 Hz, 2H, ArH), 7.47 (d, J ¼ 8.2 Hz, 2H, ArH), 7.12
(d, J ¼ 8.0 Hz, 2H, ArH), 3.24 (d, J ¼ 5.0 Hz, 1H, CH), 2.34 (dt, J ¼ 13.5,
6.8 Hz,1H, CH), 2.24 (s, 3H, CH3), 1.60 (d, J ¼ 6.8 Hz, 3H, CH3), 1.19 (d,
J ¼ 6.8 Hz, 3H, CH3). ESI-MS: 654.1[M þ Na]þ. Anal. Calc. for
C30H26N3O4PdS(631.0): C, 57.01; H, 4.31; N, 6.61. Found: C, 57.44; H,
4.25; N, 6.61.
4.3.7. Synthesis of [Pd(dab)(TsalaNO)] (7)
The synthesis of 7 was carried out in an identical manner to 1
starting from [Pd(dab)Cl2] (15 mg, 0.056 mmol) and TsalaH2
(27 mg, 0.113 mmol). Yellow solid. IR (KBr, cmꢀ1): 1640, 1380, 579,
404, 520. 1H NMR (600 MHz, DMSO, 25 ꢁC):
d
7.93 (d, J ¼ 8.1 Hz, 2H,
4.3.3. Synthesis of [Pd(bqu)(TsleuNO)]$1.5H2O (3)
The synthesis of 3 was carried out in an identical manner to 1
starting from [Pd(bqu)Cl2] (15 mg, 0.035 mmol) and TsleuH2
(20 mg, 0.070 mmol). Yellow solid. IR (KBr, cmꢀ1): 1657, 1365, 574,
ArH), 7.35 (d, J ¼ 8.0 Hz, 2H, ArH), 4.60e4.52 (m, 1H, NH2),
4.48e4.40 (m, 1H, NH2), 4.31e4.21 (m, 2H, NH2), 3.42 (q, J ¼ 6.9 Hz,
1H, CH), 2.67e2.57 (m, 2H, CH2), 2.57e2.52 (m, 2H, CH2), 2.38 (s,
3H, CH3), 2.12e2.00 (m, 1H, CH2), 1.98e1.88 (m, 2H, CH2), 1.86e1.75
(m, 1H, CH2), 1.33 (d, J ¼ 7.0 Hz, 3H, CH3). ESI-MS: 434.1 [M ꢀ H]ꢀ.
Anal. Calc. for C14H23N3O4PdS(435.8): C, 38.58; H, 5.32; N, 9.64.
Found: C, 38.78; H, 5.04; N, 9.43.
402, 495. 1H NMR (600 MHz, DMSO, 25 ꢁC):
d
9.15 (d, J ¼ 8.4 Hz, 1H,
ArH), 9.06 (d, J ¼ 8.6 Hz, 1H, ArH), 9.00 (d, J ¼ 8.6 Hz, 1H, ArH), 8.91
(d, J ¼ 8.8 Hz, 1H, ArH), 8.82 (d, J ¼ 8.8 Hz, 1H, ArH), 8.54 (d,
J ¼ 8.9 Hz, 1H, ArH), 8.25e8.18 (m, 2H, ArH), 7.98e7.92 (m, 1H, ArH),
7.92e7.79 (m, 3H, ArH), 7.43 (d, J ¼ 8.1 Hz, 2H, ArH), 7.10 (d,
J ¼ 8.0 Hz, 2H, ArH), 3.49e3.41 (m, 1H, CH), 2.23 (s, 3H, CH3),
2.13e2.01 (m, 1H, CH), 1.14 (d, J ¼ 6.8 Hz, 3H, CH3), 1.06 (t, J ¼ 7.0 Hz,
2H, CH2), 0.74 (d, J ¼ 6.4 Hz, 3H, CH3). ESI-MS: 668.1[M -
1.5H2O þ Na]þ. Anal. Calc. for C31H32N3O5.5PdS(672.1): C, 55.32; H,
4.79; N, 6.24. Found: C, 55.33; H, 4.45; N, 6.16.
4.4. Data collection and structural refinement of the complex (7)
The data collection of the complex (7) was performed on
a Bruker SMART APEX II CCD diffractometer equipped with
a graphite monochromatized Mo K
a
radiation (
l
¼ 0.71073 Å) at
296(2)K. Multi-scan absorption corrections were applied using the
SADABS program. The structure was solved by the direct method
using the SHELXS-97 program. Refinements on F2 were performed
using SHELXL-97 by the full-matrix least-squares method with
anisotropic thermal parameters for all non-hydrogen atoms.
Table 3 lists crystallographic details. Crystallographic data for the
structural analysis of (7) have been deposited with the Cambridge
Crystallographic Data Centre, CCDC- 804827 (7). Copies of this
information may be obtained free of charge from The Director,
CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (Fax: þ44 1223
4.3.4. Synthesis of [Pd(bqu)(TsileNO)]$2H2O (4)
The synthesis of 4 was carried out in an identical manner to 1
starting from [Pd(bqu)Cl2] (15 mg, 0.035 mmol) and TsileH2 (20 mg,
0.070 mmol). Yellow solid. IR (KBr, cmꢀ1): 1612, 1365, 586, 411, 490.
1H NMR (600 MHz, DMSO, 25 ꢁC):
d
9.33 (d, J ¼ 8.8 Hz, 1H, ArH),
9.07 (d, J ¼ 8.7 Hz, 1H, ArH), 9.01 (d, J ¼ 8.6 Hz, 1H, ArH), 8.92 (d,
J ¼ 8.8 Hz, 1H, ArH), 8.84 (d, J ¼ 8.8 Hz, 1H, ArH), 8.58 (d, J ¼ 8.6 Hz,
1H, ArH), 8.25e8.16 (m, 2H, ArH), 8.00e7.92 (m, 2H, ArH),
7.90e7.82 (m, 2H, ArH), 7.47 (d, J ¼ 8.1 Hz, 2H, ArH), 7.12 (d,
J ¼ 8.0 Hz, 2H, ArH), 3.27 (d, J ¼ 5.4 Hz, 1H, CH), 2.24 (s, 3H, CH3),
2.22e2.10 (m, 2H, CH2), 1.89e1.79 (m, 1H, CH), 1.27 (d, J ¼ 6.8 Hz,