JOURNAL OF CHEMICAL RESEARCH 2010 105
7.7–7.8 (m, 1H, ArH); MS m/z (%): 314 (M+., 100), 315 (M+. + 1, 19),
316 (M+. + 2, 5), 179 (M+. –PhNCS, 18), 165 (22.5), 135 (28), 105
(4.3), 91 (22.5), 77 (61); Anal. Calcd for C20H N S (314.40); C,
76.40; H, 4.49; N, 8.91. Found: C, 76.66; H, 4.33;1N4 ,28.65%.
exchangeable); MS m/z (%): 340 (M+., 0), 323 (M+.–OH, 11.4), 322
(M+.–H2O, 47.2), 246 (4.8), 245 (M+.–(H2O + Ph), 16.7), 217 (33), 190
(76), 165 (13.5), 103 (30.3), 88 (24.4), 51 (100); Anal. Calcd for
C H16N O (340.38); C, 74.10; H, 4.74; N, 16.46. Found: C, 73.70;
H2,14.27;4N, 16.11%.
4-Phenyl-2-(pyridin-2-yl)phthalazine-1(2H)-thione (3c): 78%
yield; yellow crystals; m.p. 170–172 °C (ethanol); IR: 1664, 1581
3,6-diphenyl-[1,2,4]triazolo[3,4-a]phthalazine (6): A mixture of
compound 5a (2 mmole) and benzoyl chloride (2 mmole), in dry pyr-
idine (20 mL), was refluxed for 4 h. The reaction mixture was left to
cool, and then poured onto ice/HCl mixture. A brown precipitated
solid was obtained, filtered off and recrystallised from toluene to give
6. Compound 6 also prepared by refluxing of 5d in dry toluene for 7
h. 86% yield; pale brawn crystals; m.p. 258 - 260 °C ; IR: 1612, 1533
1
(C=N), 1309 (C=S); H NMR (DMSO-d6) δ: 7.2–7.5 (m, 6H, ArH),
7.6–7.8 (m, 6H, ArH), 8.3–8.4 (m, 1H, ArH); MS m/z (%):315 (M+.,
100), 316 (M+. + 1, 16), 317 (M+. + 2, 3), 238 (12), 237 (4), 179 (32),
165 (41.5), 105 (6.6), 91 (12.8), 77 (54); Anal. Calcd for C19H13N S
(315.39); C, 72.36; H, 4.15; N, 13.32. Found: C, 72.00; H, 4.432;
N, 13.01%.
1
(C=N); H NMR (DMSO-d6) δ: 7.1–7.2 (m, 1H, ArH), 7.4–7.9 (m,
1-Chloro-4-phenylphthalazine (4): In 100 mL R.B flask compound
2a (1g.) was heated with 10 mL POCl on boiling water bath for 5h.
Pour into ice/cold water, and then extra3ct the product by diethyl ether.
Evaporating ether under vacuum, give yellow solid, recrystallised
8H, ArH), 8.0–8.1 (m, 1H, ArH), 8.3–8.4 (m, 2H, ArH), 8.6–8.7 (m,
2H, ArH) ; MS m/z (%): 322 (M+., 3), 294 (M+.–N , 8.2), 217 (M+.–(N2
+ Ph), 2.9), 193 (0.7), 165 (9.5), 105 (100), 1152(4.7), 103 (2.1), 88
(2.1), 77 (83), 51 (43.6); Anal. Calcd for C21H14N4 (322.36); C, 78.24;
H, 4.38; N, 17.38. Found: C, 77.88; H, 4.54; N, 16.89%.
1
from toluene, m.p. 150–152 (77% yield. IR: 1675, 1617 (C=N); H
NMR (DMSO-d6) δ: 7.3–7.5 (m, 3H, ArH), 7.7–8.1 (m, 6H, ArH) ;
MS m/z (%): 240 (M+., 100), 241 (M+. + 1, 35.5), 242 (M+. + 2, 14.4),
238 (23.5). 205 (5.7), 203 (24.1), 103 (5.3), 88 (13.5); Anal. Calcd
for C14H ClN2 (240.69); C, 69.86; H, 3.77; N, 11.64. Found: C, 69.76;
H, 4.04;9N, 14.37%.
1-(3,5-dimethyl-1H-pyrazol-1-yl)-4-phenylphthalazine (7): A mix-
ture of compound 5a (2 mmole) and acetyl acetone (2 mmole), in dry
toluene (30 mL), was refluxed for 6 h. The reaction mixture was left
to cool. A yellow solid product was obtained, recrystallised from etha-
nol to give 86% yield; pale yellow crystals; m.p. 280–282 °C; IR:
1
3004 (C-H, ArH), 2908, 2857 (C–H, alkyl) 1671, 1614 (C=N); H
General procedure
NMR (DMSO-d6) δ: 2.1 (s, 3H, CH ), 2.6 (s, 3H, CH ), 5.8 (s, 1H,
pyrazol-H), 7.4–7.7 (m, 5H, ArH), 8.23–8.4 (m, 4H, ArH)3; MS m/z (%):
300 (M+., 5.6), 299 (4.1), 270 (M+.- 2CH3, 3.8), 223 (M+.- Ph, 15.8),
221 (100), 195 (4.5), 193 (7.1), 165 (37.6), 77 (22.2), 66 (6.4); Anal.
Calcd for C19H N (300.36); C, 75.98; H, 5.37; N, 18.65. Found: C,
75.46; H, 5.22;1N6 ,418.51%.
The solution of compounds 3a or 4 (2 mmole), in dry toluene (30 mL),
and an equivlant amount of hydrazine hydrate, 2-hydrazinooyridine,
thiosemicarbazide or benzoyl hydrazine, were refluxed for one hour.
A solid product was obtained after cooling, filtered off, washed with
light petroleum ether and recrystallised from the suitable solvents to
give compounds 5a–d
1-Hydrazinyl-4-phenylphthalazine (5a): 84% yield; orange crys-
tals; m.p. 270–272 °C (toluene); IR: 3368, 3301 (NH), 1563 (C=N);
1H NMR (DMSO-d6) δ: 4.3–4.4 (br. s, 2NH exchangeable), 7.2–7.8
(m, 8H, ArH), 8.8–8.9 (m, 1H, ArH) 11.9 (br. s, 1NH exchangeable);
MS m/z (%): 236 (M+., 0), 221 (M+. – NH, 21.7), 165 (20), 119 (25),
103 (23.3), 91 (100), 88 (14.1), 78 (12); Anal. Calcd for C H N
(236.27); C, 71.17; H, 5.12; N, 23.71. Found: C, 70.89; H, 41.4781;2N4,
23.37%.
1-Phenyl-4-(2-(pyridin-2-yl)hydrazinyl)phthalazine (5b): 77%
yield; yellow crystals; m.p. 268– 271 °C (ethanol); IR: 3383, 3210,
3186 (NH), 1639, 1600 (C=N); 1H NMR (DMSO-d6) δ: 6.8–6.9 (m,
1H, ArH), 7.3–7.4 (m, 1H, ArH), 7.5–8.1 (m, 9H, ArH), 8.3–8.4 (m,
1H, ArH), 8.7–8.8 (m, 1H, ArH) 12.5, 12.9 ( (br. s, 2NH exchange-
able); MS m/z (%): 313 (M+., 38.2), 314 (M+. + 1, 10.8), 312 (18.8),
311 (3.6), 298 (10), 297 (44.6), 205 (13.9), 165 (9.7), 108 (4.2), 78
(61.8), 51 (100); Anal. Calcd for C19H15N5 (313.36); C, 72.83; H, 4.82;
N, 22.35. Found: C, 72.51; H, 5.14; N, 21.91%.
2-(4-Phenylphthalazin-1-yl)hydrazinecarbothioamide (5c): 81%
yield; yellow crystals; m.p. 278–280 °C (ethanol); IR: 3314, 3212,
3120 (NH), 1602, 1568 (C=N), 1308 (C=S) ; 1H NMR (CDCl3) δ: 6.4
(br. s, 1NH exchangeable), 7.2–7.6 (m, 7H, ArH), 8.1–8.2 (m, 1H,
ArH), 8.3–8.4 (m, 1H, ArH), 8.7 (br. s, 2H, NH2 exchangeable), 11.5
(br. s, 1NH exchangeable); MS m/z (%): 295 (M+., 0), 279 (M+.–NH2,
6.4), 220 (M+.–(HNCS + NH ), 4.3), 205 (38.6), 165 (12.9), 130
(10.7), 128 (20.7), 88 (16.4), 277 (100); Anal. Calcd for C15H13N S
(295.36); C, 61.00; H, 4.44; N, 23.71. Found: C, 59.78; H, 4.156;
N, 23.53%.
Np-(4-phenylphthalazin-1-yl)benzohydrazide (5d): 86% yield; pale
yellow crystals; m.p. > 300 °C (ethanol); IR: 3303, 3191 (NH), 1660
(C=O), 1598 (C=N); 1H NMR (DMSO-d6) δ: 7.2–7.5 (m, 5H, ArH),
7.6–7.9 (m, 7H, ArH), 8.1–8.2 (m, 2H, ArH), 8.3, 11.5 (br. s, 2NH
Received 8 November 2009; accepted 4 February 2010
Paper 090867 doi: 10.3184/030823410X12658886079090
Published online: 1 March 2010
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