JOURNAL OF CHEMICAL RESEARCH 2014 113
5,5′-(Pyridine-2,6-diyl)bis(4-methyl-4H-1,2,4-triazole-3-thiol) (4a):
Yield 89%; m.p. 290–292 °C; IR (KBr) νmax/cm–1: 3101–3005 (CH-
aromatic), 2922 (CH3), 2758 (S–H), 1537, 1493 (C=N), 1273 (C=S); 1H
NMR (DMSO-d6) δ 3.32 (s, 6H, 2×ꢀCH3), 8.11–8.23 (m, 3H, py-H),
14.16 (s, 2H, SH, exchangeable with D2O). 13C NMR (DMSO-d6) δ 33.1,
125.2, 139.8, 146.0, 149.3, 169.0. Anal. calcd for C11H11N7S2: C, 43.26;
H, 3.63; N, 32.11; S, 21.00; found: C, 43.31; H, 3.71; N, 32.19; S, 21.09%.
5,5′-(Pyridine-2,6-diyl)bis(4-ethyl-4H-1,2,4-triazole-3-thiol) (4b):
Yield 90%; m.p. 285–287 °C; IR (KBr) νmax/cm–1: 3103–3005 (CH-
aromatic), 2920 (CH3), 2758 (S–H), 1577, 1537 (C=N), 1273 (C=S); 1H
NMR(DMSO-d6) δ 1.16 (t, 6H, 2×ꢀCH3, J=6.1 Hz), 4.43 (q, 4H, 2×ꢀCH2,
J=6.1 Hz), 8.12 (d, 1H, ArH, J=7.3 Hz), 8.21 (t, 2H, ArH, J=7.3 Hz),
14.17 (s, 2H, SH, exchangeable with D2O). 13C NMR (DMSO-d6) δ 14.1,
39.8, 125.7, 140.0, 146.2, 148.7, 168.3. Anal. calcd for C13H15N7S2: C,
46.83; H, 4.53; N, 29.41; S, 19.23; found: C, 46.93; H, 4.60; N, 29.47; S,
19.28%.
5,5′-(Pyridine-2,6-diyl)bis(N-ethyl-1,3,4-thiadiazol-2-amine) (5b):
Yield 90%; m.p.>300 °C; IR (KBr) νmax/cm–1: 3194 (NH), 3084 (CH-
aromatic), 2966–2847 (CH3), 1587, 1564, (C=N). 1H NMR (DMSO-d6)
δ 1.19 (t, 6H, 2×ꢀCH3, J=7.2 Hz), 3.35 (q, 4H, 2×ꢀCH2, J=7.2 Hz),
7.99–8.05 (m, 3H, ArH), 8.11 (br, 2H, NH, exchangeable with D2O). 13
C
NMR (DMSO-d6) δ (ppm): 14.6, 39.2, 119.5, 139.0, 149.8, 157.2, 170.5.
Anal. calcd for C13H15N7S2: C, 46.83; H, 4.53; N, 29.41; S, 19.23; found:
C, 46.90; H, 4.59; N, 29.48; S, 19.29%.
5,5′-(Pyridine-2,6-diyl)bis(N-phenyl-1,3,4-thiadiazol-2-amine) (5c):
Yield 89%; m.p.>300 °C; IR (KBr) νmax/cm–1: 3209 (NH), 2972 (CH-
1
Ar), 1554, 1502 (C=N); H NMR (DMSO-d6) δ 6.98–8.09 (m, 13H,
ArH), 10.62 (2H, NH, exchangeable with D2O). 13C NMR (DMSO-d6) δ
118.2, 120.3, 122.7, 129.5, 139.1, 140.8, 149.4, 158.8, 166.3. Anal. calcd
for C21H15N7S2: C, 58.72; H, 3.52; N, 22.83; S, 14.93; found: C, 58.82; H,
3.65; N, 22.88; S, 15.00%.
5,5′-(Pyridine-2,5-diyl)bis(N-methyl-1,3,4-thiadiazol-2-amine) (5d):
Yield 91%; m.p.>300 °C; IR (KBr) νmax/cm–1: 3194 (NH), 3082 (CH-
aromatic), 2964, 2901 (CH3), 1585, 1564 (C=N); 1H NMR (DMSO-d6)
δ 2.94 and 295 (br, 6H, 2×ꢀCH3), 8.10 (br, 3H, 1×ꢀArH and 2×ꢀNH,
exchangeable with D2O), 8.23 (d, 2H, ArH, J=8.3 Hz), 8.92 (s, 1H,
ArH); 13C NMR (DMSO-d6) δ 31.8, 31.9, 119.7, 127.5, 134.8, 147.2,
150.1, 152.7, 157.6, 170.4, 171.4. Anal. calcd for C11H11N7S2: C, 43.26;
H, 3.63; N, 32.11; S, 21.00; found: C, 43.29; H, 3.70; N, 32.23; S, 21.14%.
5,5′-(Pyridine-2,5-diyl)bis(N-ethyl-1,3,4-thiadiazol-2-amine) (5e):
Yield 92%; m.p.>300 °C; IR (KBr) νmax/cm–1: 3192 (NH), 3086 (CH-
5,5′-(Pyridine-2,6-diyl)bis(4-phenyl-4H-1,2,4-triazole-3-thiol)
(4c): Yield 88%; m.p.>300 °C; IR (KBr) νmax/cm–1: 3078–3016 (CH-
aromatic), 2756 (S–H), 1595, 1543 (C=N), 1276 (C=S); 1H NMR
(DMSO-d6) δ 7.05–8.00 (m, 13H, ArH),14.18 (s, 2H, SH, exchangeable
with D2O). 13C NMR (DMSO-d6) δ 126.0, 128.7, 129.0, 129.3, 134.6,
139.1, 145.1, 149.2, 169.2. Anal. calcd for C21H15N7S2: C, 58.72; H, 3.52;
N, 22.83; S, 14.93; found: C, 58.84; H, 3.68; N, 22.91; S, 14.98%.
5,5′-(Pyridine-2,5-diyl)bis(4-methyl-4H-1,2,4-triazole-3-thiol) (4d):
Yield 91%; m.p.>300 °C; IR (KBr) νmax/cm–1: 3092 (CH-aromatic),
1
aromatic), 2966, 2903 and 2849 (CH3), 1585, 1564 (C=N); H NMR
(DMSO-d6) δ 1.19 (br, 6H, 2×ꢀCH3), 3.34 (br, 4H, 2×ꢀCH2), 8.12 (br, 2H,
ArH and 2H, NH, exchangeable with D2O), 8.90 (s, 1H, ArH). 13C NMR
(DMSO-d6) δ 14.6, 14.7, 39.2, 39.3, 119.6, 127.4, 134.8, 147.2, 150.1,
152.5, 157.5, 169.4, 170.4. Anal. calcd for C13H15N7S2: C, 46.83; H, 4.53;
N, 29.41; S, 19.23; found: C, 46.89; H, 4.58; N, 29.45; S, 19.31%.
1
2912 (CH3), 2766 (S–H), 1556, 1504 (C=N), 1290 (C=S); H NMR
(DMSO-d6) δ 3.60 (s, 3H, CH3), 3.86 (s, 3H, CH3), 8.16 (d, 1H, ArH,
J=8.1 Hz), 8.37 (d, 1H, ArH, J=8.1 Hz), 9.06 (s, 1H, py-H), 14.14 (s,
2H, SH, exchangeable with D2O). 13C NMR (DMSO-d6) δ 31.2, 31.4,
122.6, 131.0, 137.6, 148.1, 152.0, 162.8, 163.4, 164.6, 182.4. Anal. calcd
for C11H11N7S2: C, 43.26; H, 3.63; N, 32.11; S, 21.00; found: C, 43.37; H,
3.75; N, 32.21; S, 21.12%.
5,5′-(Pyridine-2,5-diyl)bis(N-phenyl-1,3,4-thiadiazol-2-amine)
(5f): Yield 88%; m.p.>300 °C; IR (KBr) νmax/cm–1: 3439 (NH), 3080
1
and 2906 (CH-aromatic), 1566, 1500 (C=N); H NMR(DMSO-d6) δ
5,5′-(Pyridine-2,5-diyl)bis(4-ethyl-4H-1,2,4-triazole-3-thiol) (4e):
Yield 92%; m.p.>300 °C; IR (KBr) νmax/cm–1: 3092 (CH-aromatic),
2933 (CH3), 2758 (S–H), 1618, 1504 (C=N), 1271 (C=S); H NMR
6.98–7.66, (m, 10H, ArH), 8.18 (d, 1H, ArH, J=8.1 Hz), 8.32 (d, 1H,
ArH, J=8.1 Hz), 9.04 (s, 1H, ArH), 10.68 (2H, NH, exchangeable with
D2O). 13C NMR (DMSO-d6) δ 117.2, 118.2, 120.1, 122.7, 127.1, 127.4,
129.6, 135.5, 141.7, 141.0, 142.2, 147.8, 150.2, 154.8, 159.2 165.1, 166.3.
Anal. calcd for C21H15N7S2: C, 58.72; H, 3.52; N, 22.83; S, 14.93; found:
C, 58.83; H, 3.67; N, 22.94; S, 14.95%.
1
(DMSO-d6) δ 1.19 and 1.27 (t, 6H, 2×ꢀCH3, J=7.2 Hz), 4.08 and 4.35
(q, 2H, 2×ꢀCH2, J=7.2 Hz), 8.19 (br, 1H, ArH), 8.31 (s, 1H, ArH), 9.14
(s, 1H, ArH), 14.15 and 14.21 (s, 2H, SH, exchangeable with D2O). 13
C
NMR (DMSO-d6) δ 13.9, 14.2, 39.1, 39.3, 123.5, 124.2, 138.1, 148.4,
148.8, 149.0, 167.7, 168.7, 182.4. Anal. calcd for C13H15N7S2: C, 46.83; H,
4.53; N, 29.41; S, 19.23; found: C, 46.92; H, 4.62; N, 29.46; S, 19.30%.
5,5′-(Pyridine-2,5-diyl)bis(4-phenyl-4H-1,2,4-triazole-3-thiol)
(4f): Yield 90%; m.p.>300 °C; IR (KBr) νmax/cm-1: 3077–3026
(CH-aromatic), 2752 (S–H), 1597, 1547 (C=N), 1260 (C=S); 1H
NMR (DMSO-d6) δ 6.99–8.36 (m, 13H, ArH,), 14.18 (br, 2H, SH,
exchangeable with D2O). 13C NMR (DMSO-d6) δ 116.8, 117.6, 119.5,
123.6, 128.1, 129.6, 135.2, 140.1, 141.3, 141.8, 148.6, 151.1, 154.3, 154.9,
159.1, 164.6, 167.7. Anal. calcd for C21H15N7S2: C, 58.72; H, 3.52; N,
22.83; S, 14.93; found: C, 58.80; H, 3.62; N, 22.88; S, 14.96%.
The authors gratefully acknowledge the research committee of
Arak University for providing the financial support.
Received 15 September 2013; accepted 23 December 2013
Paper 1302199 doi: 10.3184/174751914X13896291543361
Published online: 5 February 2014
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Synthesis of 5,5′-(pyridine-2,6-diyl and pyridine-2,5-diyl)bis(2-
substituted phenyl or alkyl–1,3,4–thiadiazole-2-diamines) (5a–f):
general procedure
A solution of 3a–f (3 mmol), in concentrated sulfuric acid (3 mL)
was stirred at room temperature for 2 h and the resulting mixture was
poured into ice cold water. The solution was made alkaline to pH~8
with aqueous ammonia and the precipitate obtained filtered then
washed with water and recrystallised from DMF-H2O (2:1).
5,5′-(Pyridine-2,6-diyl)bis(N-methyl-1,3,4-thiadiazol-2-amine) (5a):
Yield 89%; m.p.>300 °C; IR (KBr) νmax/cm–1: 3188 (NH), 3094 (CH-
aromatic), 2960, 2864 (CH3), 1641, 1562 (C=N). 1H NMR (DMSO-d6)
δ 3.00 (br, 6H, 2CH3), 7.97–8.00 (m, 3H, ArH,), 8.96 (br, 2H, NH,
exchangeable with D2O). 13C NMR (DMSO-d6) δ 32.4, 120.8, 139.7,
148.1, 156.7, 170.4. Anal. calcd for C11H11N7S2: C, 43.26; H, 3.63; N,
32.11; S, 21.00; found: C, 43.35; H, 3.73; N, 32.17; S, 21.15%.
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