Month 2015
Synthesis of New Bispyranopyrazoles
(14%), 107 (11%), 94 (18%); Anal. Calcd. For C31H28N8O4:
C36H38N8O4: C, 66.86; H, 5.92; N, 17.33; Found C,
C, 64.57; H, 4.89; N,19.43; Found C, 64.62; H, 4.93; N,
19.39%.
66.90; H, 5.88; N, 17.37%.
Synthesis of 4,4′-(3,3′-(decane-1,10-diylbis(oxy))bis(3,1-
phenylene))bis(6-amino-3-methyl-1,4-dihydropyrano[2–45]pyrazole-
5-carbonitrile) 4f. The compound 4f was synthesized from
the reaction of 2f (0.01mol) with 3-methylpyrazole-5-one 3
(0.02mol) and malononitrile (0.02 mol) under the same
conditions as described earlier for 4a.
Synthesis of 4,4′-(3,3′-(hexane-1,6-diylbis(oxy))bis(3,1-
phenylene))bis(6-amino-3-methyl-1,4-dihydropyrano[2–45]pyrazole-
5-carbonitrile) 4d. The compound 4d was obtained by
treating 2d (0.01mol) with 3-methylpyrazole-5-one 3
(0.02mol) and malononitrile (0.02mol) under the same
conditions as used earlier for 4a.
4f: Light brown solid; Yield 76%; m.p.: 96–98°C. IR
(KBr) cmꢀ1 3350 and 3222 (NH2), 3149 (NH), 2933, 2844
(methylene C―H), 2253 (CN), 1599 (C¼N), 1250, 1042
(C―O); 1H-NMR (400MHz, CDCl3): δ 11.14 (2H, s, NH),
7.10 (2H, d, Jo =7.5Hz, H-6′), 7.04 (2H, t, Jo =7.3Hz, H-
5′), 6.98 (2H, dd, Jo = 7.4, 2.3Hz, H-4′), 6.86 (2H, brs, H-
2′), 6.69 (4H, s, NH2), 5.09 (1H, s, H-4), 4.13 (4H, t,
Jvic =5.9Hz, OCH2), 2.02 (2H, q, Jvic =4.6Hz, OCH2CH2),
1.79 (6H, s, CH3), 1.51 (12H, m, OCH2CH2CH2CH2CH2);
13C-NMR (400MHz, CDCl3): δ 162.41 (C-6), 157.72
(C-3′), 139.09 (C-3), 136.16 (C-1′), 135.35 (C-7a), 129.21
(C-6′), 125.26 (C-5′), 117.18 (C≡N), 116.40 (C-3a), 113.13
(C-4′), 111.25 (C-2′). 65.12 (OCH2), 57.60 (C-5), 35.59
(C-4), 28.61 (OCH2CH2), 25.31 (OCH2CH2CH2), 22.10
(OCH2CH2CH2CH2), 19.11 (OCH2sCH2CH2CH2CH2); 9.54
(CH3); ESI-MS: m/z 697 (M +Na, 100%), 675 (M+1,
56%), 642 (17%), 584 (9%), 568 (12%), 493 (14%), 472
(11%), 398 (29%), 302 (14%), 214 (4%), 121 (21%), 93
(12%); Anal. Calcd. For C38H42N8O4: C, 67.64; H, 6.27; N,
4d: Brown solid; Yield 80%; m.p.: 122–124°C; IR
(KBr) cmꢀ1 3391 and 3214 (NH2), 3140 (NH), 2935,
2865 (methylene C―H), 2257 (CN), 1595 (C¼N), 1251,
1
1088 (C―O); H-NMR (400 MHz, CDCl3): δ 11.32 (2H,
s, NH), 7.28 (2H, d, Jo = 7.4 Hz, H-6′), 7.19 (2H, t,
Jo = 7.1Hz, H-5′), 7.11 (2H, d, Jo = 7.2 Hz, H-4′), 6.93
(2H, brs, H-2′), 6.78 (4H, s, NH2), 5.20 (1H, s, H-4),
4.19 (4H, t, Jvic = 6.6 Hz, OCH2), 2.11 (4H, q,
Jvic =6.4 Hz, OCH2CH2), 1.92 (4H, m, OCH2CH2CH2),
1.73 (6H, s, CH3); 13C-NMR (400 MHz, CDCl3): δ
162.46 (C-6), 157.80 (C-3′), 139.11 (C-3), 136.21 (C-1′),
135.40 (C-7a), 129.28 (C-6′), 125.29 (C-5′), 117.20
(C≡N), 116.38 (C-3a), 113.33 (C-4′), 111.30 (C-2′). 64.39
(OCH2), 57.68 (C-5), 35.52 (C-4), 29.13 (OCH2CH2),
21.78 (OCH2CH2CH2), 9.67 (CH3); ESI-MS: m/z 641 (M
+Na, 24%), 619 (M+1, 26%), 590 (19%), 538 (12%), 493
(14%), 462 (11%), 398 (29%), 270 (14%), 242 (100%),
122 (21%), 108 (4%); Anal. Calcd. For C34H34N8O4: C,
66.01; H, 5.54; N,18.11; Found C, 65.97; H, 5.59; N,
16.61; Found C, 67.69; H, 6.31; N, 16.65%
Synthesis of 4,4′-(3,3′-(dodecane-1,12-diylbis(oxy))bis(3,1-
phenylene))bis(6-amino-3-methyl-1,4-dihydropyrano[2–45]pyrazole-
18.15%.
Synthesis of 4,4′-(3,3′-(octane-1,8-diylbis(oxy))bis(3,1-phenylene))
bis(6-amino-3-methyl-1,4-dihydropyrano[2–45]pyrazole-5-car
bonitrile) 4e. The compound 4e was prepared from the
reaction of 2e (0.01 mol) with 3-methylpyrazole-5-one 3
(0.02 mol) and malononitrile (0.02 mol) under the same
conditions as described above for 3a.
5-carbonitrile) 4g.
The compound 4g was obtained by
reacting 2g (0.01mol) with 3-methylpyrazole-5-one 3
(0.02mol) and malononitrile (0.02mol) under the same
conditions used earlier for 4a.
4g: Grey solid; Yield 68%; m.p.: 104–106°C; IR (KBr)
cmꢀ1 3359 and 3228 (NH2), 3145 (NH), 2938, 2851 (meth-
ylene C―H), 2257 (CN), 1598 (C¼N), 1252, 1044 (C―O);
1H-NMR (400MHz, CDCl3): δ 11.09 (2H, s, NH), 7.09 (2H,
d, J=7.0Hz, H-6′), 7.02 (2H, t, Jo =7.3Hz, H-5′), 6.95
(2H, d, Jo =7.6Hz, H-4′), 6.82 (2H, brs, H-2′), 6.65
(4H, s, NH2), 5.03 (1H, s, H-4), 3.80 (4H, t, Jvic =6.1Hz,
OCH2), 1.68 (2H, q, Jvic =6.6Hz, OCH2CH2), 1.77 (3H, s,
CH3), 1.22 (16H, m, CH2CH2CH2CH2CH2CH2); 13C-
NMR (400MHz, CDCl3): δ 162.40 (C-6), 157.69 (C-3′),
139.08 (C-3), 136.10 (C-1′), 135.31 (C-7a), 129.19 (C-6′),
125.21 (C-5′), 117.15 (C≡N), 116.40 (C-3a), 113.11
(C-4′), 111.30 (C-2′). 64.42 (OCH2), 57.70 (C-5), 35.54
(C-4), 2925.45 (OCH2CH2), 25.34 (OCH2CH2CH2), 23.21
(OCH2CH2CH2CH2), 19.11 (OCH2CH2CH2CH2CH2),
15.01 (OCH2CH2CH2CH2CH2CH2), 9.67 (CH3); ESI-MS:
m/z 725 (M+Na, 21%), 703 (M+1, 13%), 629 (4%), 581
(9%), 527 (8%), 428 (5%), 372 (4%), 372 (7%), 313
(19%), 294 (15%), 239 (11%), 162 (13%). 107 (11%); Anal.
Calcd. For C40H46N8O4: C, 68.35; H, 6.60; N, 15.94; Found
C, 68.39; H, 6.56; N, 15.89%.
4e: Brown solid; Yield 65%, m.p.: 130–132°C; IR
(KBr) cmꢀ1 3364 and 3210 (NH2), 3145 (NH), 2938,
2867 (methylene C―H), 2250 (CN), 1598 (C¼N), 1249,
1
1086 (C―O); H-NMR (400 MHz, CDCl3): δ 11.21 (2H,
s, NH), 7.22 (2H, d, Jo = 7.8 Hz, H-6′), 7.13 (2H, t,
Jo = 7.1Hz, H-5′), 7.09 (2H, d, Jo = 7.0 Hz, H-4′), 6.92
(2H, s, H-2′), 6.81 (4H, s, NH2), 5.29 (1H, s, H-4), 4.24
(4H, t, Jvic = 6.5 Hz, OCH2), 1.86 (4H, quintet,
Jvic =6.5 Hz, OCH2CH2), 1.46 (4H, quintet, Jvic = 5.3 Hz,
OCH2CH2CH2), 1.35 (4H, m, OCH2CH2CH2CH2), 1.81
(6H, s, CH3); 13C-NMR (400 MHz, CDCl3): δ 162.30
(C-6), 157.72 (C-3′), 139.1 (C-3), 136.02 (C-1′), 135.29
(C-7a), 129.20 (C-6′), 125.18 (C-5′), 117.09 (C≡N),
116.33 (C-3a), 113.32 (C-4′), 111.23 (C-2′). 64.36
(OCH2), 57.61 (C-5), 35.49 (C-4), 29.15 (OCH2CH2),
24.21 (OCH2CH2CH2), 17.10 (OCH2CH2CH2CH2), 9.58
(CH3); ESI-MS: m/z 668 (M+ Na, 19%), 647 (M +1,
16%), 642 (17%), 628 (13%), 586 (9%), 572 (12%), 516
(11%), 474 (14%), 473 (11%), 398 (29%), 214 (5%), 121
(10%), 108 (16%), 94 (12%); Anal. Calcd. For
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet