M.A.E.A.A.A. El-Remaily, S.K. Mohamed / Tetrahedron xxx (2013) 1e6
5
2H), 2.24e1.32 (m, 30H), 1.20 (9, 2H), 0.91 (t, 3H); 13C NMR
precipitated on hot, filtered off, washed with water, and recrystal-
(300 MHz, DMSO-d6):
d
162.8, 159.7, 53.5, 32.1, 29.8e29.3 (10C),
lized from ethanol.
27.1, 24.9, 19.8, 13.1; ESI MS (m/z): 379.58 (Mþ).
4.3.1. 5-(2H-1,2,3,4-Tetraazol-5-ylmethyl)-2H-1,2,3,4-tetraazole
4.2.6. 1-(2-Adamantan-1-yl-2H-tetrazol-5-yl)guanidine
14. Yield
30. Yield 82%, Mp >320 ꢁC. FTIR (KBr, cmꢃ1): 3384, 3275, 3118; 1H
87%, Mp 242e245 ꢁC. FTIR (KBr, cmꢃ1): 3395, 3284, 3160, 2895; 1H
NMR (300 MHz, DMSO-d6):
d
8.56 (s, 2H, 2NH), 3.89 (s, 2H, CH2);
153.2, 22.4; ESI MS (m/z): 152.12
NMR (300 MHz, DMSO-d6):
d
6.89 (s, 4H), 3.05 (m, 6H), 2.07 (m,
13C NMR (300 MHz, DMSO-d6):
d
3H), 1.64 (m, 6H); 13C NMR (300 MHz, DMSO-d6):
61.3, 38.6, 37.4, 26.1; ESI MS (m/z): 261.32 (Mþ).
d
163.1, 159.8,
(Mþ).
4.3.2. Ethyl 2-(2H-1,2,3,4-tetraazol-5-yl)acetate 31. Yield 85%, Mp
>320 ꢁC. FTIR (KBr, cmꢃ1): 3388, 3271, 3114, 1726; 1H NMR
4.2.7. 2-[5-Amino(imino)methylamino-2H-1,2,3,4-tetraazol-2-yl]-
3,5-di(methylcarbony-loxy)-6-methylcarbonyloxymethyltetrahydro-
2H-4-pyranyl acetate 2-(4-bromo-phenyl)-4,5-diphenyl-1H-imidaz-
ole 15. Yield 90%, Mp 294e296 ꢁC. FTIR (KBr, cmꢃ1): 3387, 3275,
(300 MHz, DMSO-d6):
d 8.54 (s, 1H, NH), 4.05 (q, 2H, CH2), 3.47 (s,
2H, CH2), 1.22 (t, 3H, CH3); 13C NMR (300 MHz, DMSO-d6):
151.1, 60.2, 38.7, 14.1; ESI MS (m/z): 156.14 (Mþ).
d 164.2,
3115, 1724; 1H NMR (300 MHz, DMSO-d6):
d
7.1 (d, 1H), 6.89 (s, 4H),
6.04 (t,1H), 5.34 (t,1H), 5.14 (t,1H), 4.32 (d, 2H), 4.11 (m,1H), 2.11 (s,
3H), 2.00 (s, 3H), 1.96 (s, 6H); 13C (300 MHz, DMSO-d6): 171.1,
4.3.3. 2-Phenyl-1,1-di(2H-1,2,3,4-tetraazol-5-yl)ethylene 32. Yield
80%, Mp >320 ꢁC. FTIR (KBr, cmꢃ1): 3388, 3273, 3121, 1611; 1H NMR
d
169.9, 168.2, 163.1, 159.7, 93.2, 67.9, 66.2, 66.0, 64.4, 61.8, 20.7, 20.5,
(300 MHz, DMSO-d6): d 8.67 (s, 2H, 2NH), 7.81e7.42 (m, 5H, arom),
20.3; ESI MS (m/z): 461.43 (Mþ).
7.12 (s,1H, CH); 13C NMR (300 MHz, DMSO-d6):
d 154.4,150.8,138.6,
132.3, 131.5, 128.8, 117.2; ESI MS (m/z): 240.23 (Mþ).
4.2.8. N5-Amino(imino)methyl-2-2-[5-amino(imino)methylamino-
2H-1,2,3,4-tetraazol-2-yl]ethyl-2H-1,2,3,4-tetraazol-5-amine
21. Yield 85%, Mp 300e302 ꢁC. FTIR (KBr, cmꢃ1): 3387, 3261, 3114;
4.3.4. Ethyl (E)-3-phenyl-2-(2H-1,2,3,4-tetraazol-5-yl)-2-propenoate
33. Yield 84%, Mp >320 ꢁC. FTIR (KBr, cmꢃ1): 3387, 3270, 3129,
1H NMR (300 MHz, DMSO-d6):
d
6.69 (s, 8H, 4NHþ2NH2), 5.61 (s,
1727, 1611; 1H NMR (300 MHz, DMSO-d6):
d
8.63 (s, 1H, NH),
7.80e7.42 (m, 5H, arom), 7.18 (s, 1H, CH), 4.10 (q, 2H, CH2), 1.25 (t,
3H, CH3); 13C NMR (300 MHz, DMSO-d6):
162.1, 152.9,
4H, 2CH2); 13C NMR (300 MHz, DMSO-d6):
MS (m/z): 280.25 (Mþ).
d 163.2, 159.7, 48.3; ESI
d
150.1, 138.2, 132.0, 131.1, 128.5, 117.0, 61.6, 13.9; ESI MS (m/z):
4.2.9. N5-Amino(imino)methyl-2-2-[5-amino(imino)methylamino-
2H-1,2,3,4-tetraazol-2-ylmethyl]benzyl-2H-1,2,3,4-tetraazol-5-amine
22. Yield 87%, Mp >320 ꢁC. FTIR (KBr, cmꢃ1): 3882, 3276, 3160; 1H
244.25 (Mþ).
Acknowledgements
NMR (300 MHz, CDCl3):
d 7.81e7.15 (m, 4H), 6.65 (s, 8H,
4NHþ2NH2), 5.53 (s, 4H, 2CH2); 13C NMR (300 MHz, CDCl3):
The authors are deeply gratitude Granada University in Spain,
Sohag University in Egypt and Manchester Metropolitan University
in England for supporting and facilitating this study.
d
162.9, 159.8, 141.1, 133.9, 132.6, 55.5; ESI MS (m/z): 356.35 (Mþ).
4.2.10. N5-Amino(imino)methyl-2-3-[5-amino(imino)methylamino-
2H-1,2,3,4-tetraazol-2-ylmethyl]benzyl-2H-1,2,3,4-tetraazol-5-amine
23. Yield 90%, Mp >320 ꢁC. FTIR (KBr, cmꢃ1): 3889, 3284, 3124; 1H
References and notes
NMR (300 MHz, CDCl3):
d 8.19 (s, 1H), 7.80e7.22 (m, 3H), 6.76
(s, 8H, 4NHþ2NH2), 5.38 (s, 4H, 2CH2); 13C NMR (300 MHz, CDCl3):
d
163.4, 158.8, 148.3, 134.1, 132.2, 131.8, 58.9; ESI MS (m/z):
356.35 (Mþ).
4.2.11. N5-Amino(imino)methyl-2-3,5-di[5-amino(imino)methyl-
amino-2H-1,2,3,4-tetraazol-2-ylmethyl]-2,4,6-trimethylbenzyl-2H-
1,2,3,4-tetraazol-5-amine 24. Yield 90%, Mp >320 ꢁC. FTIR (KBr,
ꢀ
cmꢃ1): 3887, 3272, 3132; 1H NMR (300 MHz, CDCl3):
d 6.81 (s, 12H,
6NHþ3NH2), 5.25 (s, 6H, 3CH2), 2.10 (s, 9H, 3CH3); 13C NMR
(300 MHz, CDCl3): d 163.1, 159.2, 132.9, 124.7, 51.8, 18.2; ESI MS (m/
z): 537.55 (Mþ).
4.2.12. N5-Amino(imino)methyl-2-2,4,5-tri[5-amino(imino)methyl-
amino-2H-1,2,3,4-tetraazol-2-ylmethyl]benzyl-2H-1,2,3,4-tetraazol-
5-amine 25. Yield 87%, Mp 290e292 ꢁC. FTIR (KBr, cmꢃ1): 3880,
3266, 3242; 1H NMR (300 MHz, CDCl3):
d 8.87 (s, 2H, 2CH arom),
6.65 (s, 16H, 8NHþ4NH2), 5.53 (s, 8H, 4CH2); 13C NMR (300 MHz,
CDCl3): d
163.1, 158.4, 144.2, 136.6, 55.8; ESI MS (m/z): 634.59 (Mþ).
4.3. General procedure for 5-substituted 1H-tetrazoles 30e33
mixture of sodium azide (6 mmol) and malononitrile
A
(2 mmol), ethyl cyanoacetate (1 mmol), benzylidene malononitrile
or ethyl (2E)-2-cyano-3-phenylacrylate (1 mmol) was taken in
presence of ZnBr2 or glacial AcOH in water (15 mL). The reaction
mixture was irradiated by microwave and monitored by TLC till
completion after 10 mine25 min (see Table 1). The product was