## 3 Experimental
### Chemistry
#### 3.1.2. Synthesis of Bipyridine Derivatives **8** and **9**  
A mixture of 3-acetyllypyrazole derivative **1** (0.668 g, 2 mmol), terephthalalaldehyde **7** (0.134 g, 1 mmol), and malononitrile **3** or ethyl acetoacetate **5** (2 mmol) in acetic acid (30 mL) containing ammonium acetate (1.232 g, 16 mmol) was refluxed for 8 h. After cooling the reaction mixture it was poured into an ice-water mixture, the formed a precipitate that was collected by filtration, then crystallized from dioxane to give the bipyridine products **8** and **9**, respectively. _Diethyl 3,3\({}^{\prime}\)-(1,4-phenylenebis(6-amino-5-cyanopyridine-4,2-diyl))bis(1,5-diphenyl-1H-pyrazol-4-carboxylate)_  
**(8)**. Brown solid, (68% yield), mp 187-189 \({}^{\circ}\)C; IR (KBr) \(\
u_{\rm max}\) 3378, 3201 (NH\({}_{2}\)), 2211 (CN), 1709 (C=O) cm\({}^{-1}\); \({}^{1}\)H NMR (DMSO-\(d_{6}\)) 8 1.03 (t, J = 7.2 Hz, 6H, 2 CH\({}_{3}\)), 4.14 (q, J = 7.2 Hz, 4H, 2 CH\({}_{2}\)), 6.93 (s, br, 4H, 2 NH\({}_{2}\)), 7.18-7.49 (m, 20H, Ar-H), 7.85 (s, 4H, Ar-H), 8.10 (s, 2H, 2 Pyridine-H3); MS \(m/z\) (%) 892 (M\({}^{+}\), 39), 724 (48), 622 (63), 368 (39), 82 (60), 76 (57), 43 (100). Anal. Calcd. for C\({}_{54}\)H\({}_{40}\)N\({}_{10}\)O\({}_{4}\) (892.98): C, 72.63; H, 4.52; N, 15.69. Found: C, 72.69; H, 4.36; N, 15.47%. _Diethyl 3,3\({}^{\prime}\)-(1,4-phenylenebis(5-acetyl-6-oxo-1,6-dihydropyridine-4,2-diyl))bis(1,5-diphenyl-1H-pyrazol-4-carboxylate)_ (9). Brown solid, (66% yield), mp 207-209 \({}^{\circ}\)C; IR (KBr) \(\
u_{\rm max}\) 3423 (NH), 1723, 1677, 1653 (3C=O) cm\({}^{-1}\); \({}^{1}\)H NMR (DMSO-\(d_{6}\)) 8 1.11 (t, J = 7.2 Hz, 6H, 2 CH\({}_{3}\)), 2.58 (s, 6H, 2 CH\({}_{3}\)), 4.14 (q, J = 7.2 Hz, 4H, 2 CH\({}_{2}\)), 7.24-7.48 (m, 2 OH, Ar-H), ), 7.77 (s, 2H, 2 Pyridine-H3), 7.81 (s, 4H, Ar-H), 10.06 (s, br, 2H, 2 NH); MS \(m/z\) (%) 929 (M\({}^{+}\), 17), 776 (41), 509 (37), 386 (55), 267 (40), 148 (32), 77 (100), 43 (68). Anal. Calcd. for C\({}_{56}\)H\({}_{44}\)N\({}_{6}\)O\({}_{8}\) (929.00): C, 72.40; H, 4.77; N, 9.05. Found: C, 72.17; H, 4.62; N, 9.01%. 1.3. Synthesis of 1,5-Diphenyl-1,5-dihydro-[1,2,4]triazoleolo[4,3-\(a\)]pyrimidine derivatives **15a-h**  
General procedure: Triethylamine (0.14 mL, 1 mmol) was added to a mixture of equimolar amounts of thione **11** (0.480 g, 1 mmol) and the appropriate hydrazonoyl halides **12a-h** (1 mmol) in dioxane (20 mL) at room temperature. The reaction mixture was then refluxed for 10-15 h until all hydrogen sulfide gas stopped evolving. The solid that formed after concentration of the reaction mixture was filtered and crystallized from the proper solvent to give the products **15a-h**, respectively. _Ethly 3-(3-acetyl-1,5-diphenyl-1,5-dihydro-[1,2,4]triazoleolo[4,3-\(a\)]pyrimidine-7-yl)-1,5-diphenyl-1H-pyrazol-4-carboxylate_**(15a)**. Yellow solid, (74% yield), mp 233-235 \({}^{\circ}\)(DMF); IR (KBr) \(\
u_{\rm max}\) 3026, 2956 (C-H), 1706, 1649 (2C=O), 1595 (C=N) cm\({}^{-1}\); \({}^{1}\)H NMR (DMSO-\(d_{6}\)) 8 1.15 (t, J = 7.2 Hz, 3H, CH\({}_{3}\)), 2.43 (s, 3H, CH\({}_{3}\)), 4.19 (q, J = 7.2 Hz, 2H, CH\({}_{2}\)), 5.33 (d, J = 4 Hz, 1H, CH), 6.62 (d, J = 4 Hz, 1H, CH), 7.03-7.80 (m, 20H, Ar-H); MS \(m/z\) (%) 606 (M\({}^{+}\), 5),406 (36), 287 (29), 247 (75), 194 (37), 92 (71), 65 (60), 43 (100). Anal. Calcd. for C\({}_{37}\)H\({}_{30}\)N\({}_{6}\)O\({}_{3}\) (606.69): C, 73.25; H, 4.98; N, 13.85. Found: C, 73.07; H, 4.84; N, 13.67%. _Ethly 3-(3-acetyl-5-phenyl-1-(p-tolyl)-1,5-dihydro-[1,2,4]triazoleolo[4,3-\(a\)]pyrimidine-7-yl)-1,5-diphenyl-1H-pyrazol-4-carboxylate_**(15b)**. Yellow solid, (72% yield), mp 211-213 \({}^{\circ}\)(DMF); IR (KBr) \(\
u_{\rm max}\) 3030, 2951 (C-H), 1697, 1642 (2C=O), 1597 (C=N) cm\({}^{-1}\); \({}^{1}\)H NMR (DMSO-\(d_{6}\)) 8 1.04 (t, J = 7.2 Hz, 3H, CH\({}_{3}\)), 2.24 (s, 3H, CH\({}_{3}\)), 2.44 (s, 3H, CH\({}_{3}\)), 4.16 (q, J = 7.2 Hz, 2H, CH\({}_{2}\)), 5.32 (d, J = 4 Hz, 1H, CH), 6.61 (d, J = 4 Hz, 1H, CH), 7.05-7.73 (m, 19H, Ar-H); MS \(m/z\) (%) 620 (M\({}^{+}\), 7), 498 (27), 390 (35), 285 (60), 105 (41), 77 (100), 43 (92). Anal. Calcd.