202
M. A. Mohamed
Vol 49
Scheme 3
10a. Colorless crystals, from Dioxan, yield (71%), m.p.
280–82ꢀC; mmax (cmꢁ1) (KBr) 3320, 3180 (NH2), 2184 (CN),
1663 (C¼¼N); 1H NMR (200 MHz, (CD3)2SO): d ¼ 6.92 (s,
br, 2H, NH2), 7.34–9.33 (m, 6H, aromatic); m/z 252 (Calcd.
for C13H8N4S (252.29): C, 61.89; H, 3.20; N, 22.21; S,
12.71% Found C, C, 62.00; H, 3.33; N, 22.12; S, 12.93%.
10b. Colorless crystals, from Dioxan, yield (85%), m.p.
270–72ꢀC; mmax (cmꢁ1) (KBr) 3320, 3180 (NH2), 1672 (CO),
1622 (C¼¼N); 1H NMR (200 MHz, (CD3)2SO): d ¼ 2.30
(t, 3H, CH2CH3), 3.81 (q, 2H, CH2CH3), 6.54 (s, br, 2H,
NH2), 7.33–9.33 (m, 6H, aromatic); m/z 299 (Calcd for
C15H13N3O2S (299.35): C, 60.19; H, 4.38; N, 14.04; S,
10.71% Found: C, 60.00; H, 4.45; N, 14.17; S, 10.94%.
10c. Colorless crystals, from EtOH, yield (78%), m.p. 210–
12ꢀC; mmax (cmꢁ1) (KBr) 3360, 3180 (NH2), 1700 (CO), 1599
1
spectrometer for solutions in (CD3)2SO using Si(CH3)4 as an
internal standard. Mass spectra were recorded on a Varian
MAT 112 spectrometer. Analytical data were measured at the
Microanalytical Data Center at Cairo University.
Sodium salt of 3-hydroxy-1-(pyridin-3-yl)prop-2-en-1-one
(1). A mixture of (0.01 mol) 3-acetyl pyridine and (0.01 mol)
ethyl format was dropped over a solution of (0.01 mol) of
sodium methoxide in 65-mL dry ether with stirring. The
formed solid product was collected and used directly in the
following reactions.
(C¼¼N); H NMR (200 MHz, (CD3)2SO): d ¼ 7.01 (s, br, 2H,
NH2), 7.27–7.55 (m, 5H, C6H5), 7.80–9.13 (m, 6H, aromatic);
m/z 331 (Calcd for C19H13N3OS (331.40): C, 68.86; H, 3.95;
N, 12.68; S, 9.68% Found C, 68.65; H, 4.13; N, 12.74; S,
9.53%.
6-(Pyridin-3-yl)-1H-pyrazolo[3,4-b]pyridin-3-ylamines
(13a, b). A solution of (0.01 mol) bipyridine 7 and (0.01 mol)
hydrazines 11 was refluxed in ethanol containing a catalytic
amount of pip. for 3 h. The solution was poured over ice-water
mixture and then neutralized by HCl. The solid products were
filtered off and recrystallized from water.
13a. Colorless crystals, from water, yield (77%), m.p. 105–
106ꢀC; mmax (cmꢁ1) (KBr) 3350, 2316, 2189 (NH, NH2), 1627
(C¼¼N); 1H NMR (200 MHz, (CD3)2SO): d ¼ 6.52 (s, 2H,
NH2), d ¼ 10.31 (s, br., H, NH), 7.26–9.63 (m, 6H, aromatic);
m/z 211 (Calcd. for C11H9N5 (211.22): C, 62.55; H, 4.29; N,
33.16% Found: C, 62.35; H, 4.12; N, 33.32%).
13b. Colorless crystals, from water, yield (80%), m.p. 110–
112ꢀC; mmax (cmꢁ1) (KBr) 3350, 2316 (NH2), 1627 (C¼¼N);
1H NMR (200 MHz, (CD3)2SO): d ¼ 5.21 (s, br., 2H, NH2),
7.26–8.87 (m, 11H, aromatic); m/z 211; m/z 287 (Calcd for
C17H13N5: C, 71.07; H, 4.56; N, 24.37% Found C, 71.07; H,
4.56; N, 24.37%).
1,6-Dihydro-[2,30]bipyridinyl-5-carbonitriles (5a, b). A
solution of (0.01 mol) sodium salt of 3-hydroxy-1-pyridin-3-
yl-propenone 1, (0.01 mol) cyanamides 2, (1 mL) piperidine
acetate in (3 mL) water was refluxed for 10 min. Acetic acid
(1 mL) was added to the hot solution. The solid product was
filtered off and recrystallized from the appropriate solvent.
5a. Pale yellow crystals, from DMF, (yield 70%), m.p.
230ꢀC, mmax (cmꢁ1) (KBr) 3350 (NH), 2211 (CN), 1680 (CO),
1
1622 (C¼¼N); H NMR (200 MHz, (CD3)2SO): d ¼ 6.88–8.99
(m, 6H, aromatic), 9.05 (s, br., 1H, NH); m/z 197 (Calcd. for
C11H7N3O (197.19): C, 67.00; H, 3.58; N, 21.31% Found C,
67.14; H, 3.65; N, 21.11%).
5b. Pale yellow crystals, from ethanol, yield (73%), m.p.
230–32ꢀC; mmax (cmꢁ1) (KBr) 2218 (CN); 1H NMR (200
MHz, (CD3)2SO): d ¼ 7.14–8.92 (m, 6H, aromatic), 14.25
(s, br., 1H, SH); m/z 213 (Calcd. for C11H7N3S (213.26): C,
61.95; H, 3.31; N, 19.70; S, 5.03% Found C, 62.12; H, 3.22;
N, 19.80; S, 15.11%).
6-Methylsulfanyl-[2,30]bipyridinyl-5-carbonitrile (7). Equimolar
amounts of bipyridine derivative 5b and iodomethane were
stirred in methanolic potassium hydroxide solution for 1 h.
The solution was poured over ice-water mixture and then
neutralized by HCl. The solid product was filtered off and
recrystallized from ethanol.
Colorless crystals, from EtOH, yield (71%), m.p. 170–72ꢀC;
mmax (cmꢁ1) (KBr) 2210 (CN), 1665 (C¼¼N); 1H NMR (200
MHz, (CD3)2SO): d ¼ 2.75 (s, 3H, SCH3), 7.27–9.31 (m, 6H,
aromatic); m/z 227 (Calcd. for C12H9N3S (227.28): C, 63.41;
H, 3.99; N, 18.49; S, 14.11% Found: C, 63.31; H, 4.12; N,
18.35; S, 14.00%).
3-Amino-6-(pyridin-3-yl)thieno[2,3-b]pyridines (10a–c). A
mixture of (0.01 mol) bipyridine 5b, (0.01 mol) active methyl-
enes 8 and (0.01 mol) KOH was stirred in methanol for 1 h.
The solution was poured over ice-water mixture and then
neutralized by HCl. The solid products were filtered off and
recrystallized from the appropriate solvent.
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Journal of Heterocyclic Chemistry
DOI 10.1002/jhet