ORDER
REPRINTS
114
HUANG AND ZHU
by filtration. IR ν cm−1 1654, 1500, 1410, 1360, 1280, 1000, 817, 760, 700. The
loading of capacity of the polymer was obtained by iodometry. The functional
group is 1.99 mmol/g.
Typical Procedure for Preparation of
1,3-Disubstituted-2-pyrazoline-5-carbonitriles 2
CPSID (1.2 mmol) was added at –10◦C to a stirred suspension of 1 mmol of
aldehyde hydoazone 1 in 5 mL acrylonitrile under an N2 atmosphere. The starting
material disappearance (monitored by TLC) was about 4 h. The reaction mixture
was filtrated and the liquid was concentrated under vacuum. To the residue was
added 20 mL CH2Cl2 and the organic layer was washed with 10 mL 5% aq.
Na2CO3 solution, 10 ml H2O, and dried over MgSO4. After evaporation of the
solvent, the crude material was purified by column chromatograph on silica gel
using CH2Cl2-petroleum ether (1:1) as eluent.
1
2a: White solid; mp 145◦–147◦C (lit (7) 145◦–147◦C); H-NMR (CDCl3)
δ: 8.0–7.3 (m, 10H, ArH), 5.0 (t, J 8 Hz, 5-H), 3.7 (d, J 8 Hz, 2H, 4-H); IR (KBr)
+
ν (cm−1); 2234 (C N), 1600 (C N); MS: m/z (relative intensity) 247 (M 100),
==
≡
220 (39), 194 (17), 91 (82), 77 (61).
2b: White solid: mp 147◦–148◦C (lit (7) 145◦–147◦C); H-NMR (CDCl3)
1
δ: 7.8–6.9 (m, 9H, ArH), 4.9 (t, J 8 Hz, 1H, 5-H), 3.8 (s, 3H, OCH3), 3.6 (d, J
8 Hz, 2H, 4H); IR (KBr) ν (cm−1), 2240 (C N), 1605 (C N). MS: m/z (relative
==
≡
intensity) 277 (M+ 100), 250 (61), 224 (7), 91 (48), 77 (28).
2c:Yellowsolid;mp209◦–211◦C(lit(7)209◦–211◦C);1H-NMR(d6-DMSO)
δ: 8.4–8.10 (m, 4H, ArH) δ: 7.4–7.1 (m, 5H, ArH), 5.80 (q, J 9 Hz, 1H, 5-H) 3.9
(t, J 9 Hz, 2H, 4H); IR (KBr) ν (cm−1): 1605 (C N); MS m/z (relative intensity)
==
292 (M+100), 265 (31), 91 (70), 77 (47).
2d: Greenish solid; mp 154◦–156◦C (lit (7) 154◦–156◦C); 1H-NMR (CDCl3)
==
δ: 7.8–6.6 (m., 12H, ArH, -CH CH-), 4.9 (t, J 8 Hz, 1H, 5-H), 3.4 (d, J 8 Hz, 2H,
+
4-H) IR (KBr) ν (cm−1): 1610 (C N); MS m/z (relative intensity) 273 (M 100),
==
245 (44), 220 (23), 91 (31), 77 (32).
2e: White solid; mp 140◦–142◦C; 1H-NMR (CDCl3) δ: 7.9–7.4 (m, 9H, ArH)
5.1 (t, J 8 Hz, 1H, 5-H), 3.7 (d, J 8 Hz, 2H, 4-+H); IR (KBr) ν (cm−1): 2240 (C N);
≡
==
1610 (C N); MS m/z (relative intensity) M 281 (83.85), 254 (83.62), 91 (100),
77 (83.01). Anal. Calcd for C16H12N3Cl: C, 68.21; H, 4.29; N, 14.91. Found: C,
68.43; H, 4.32; N, 14.68.
1
2f: White solid; mp 133◦–134◦C; H-NMR (CDCl3) δ: 7.9–7.5 (m, 9H,
ArH), 5.0 (t, J 8 Hz, 1H, 5-H), 3.8 (d, J 8 Hz, 2H, 4-H) IR (KBr) ν (cm−1): 1610
+
==
(C N): MS m/z (relative intensity) 281 (M 84), 254 (30), 91 (100), 77 (65) Anal.
Calcd for C16H12N3Cl: C, 68.21; H, 4.29; N, 14.91. Found: C, 67.81; N, 14.38; H:
4.15.