2-METHYL-1,2,3-TRIAZOL-4-YL(3-PHENYL-1,2,4-OXADIAZOL-5-YL)-DINITROMETHANE
315
the groups CH2 (4.17) and CH3 (2.90 ppm) were observ-
ed. Electron absorption spectra were distinguished by the
presence of two definite absorption bands with the
maxima at 235 nm (local excitation of π-electrons) and
372–375 nm (intramolecular charge transfer to the nitro
group) characteristic of conjugated nitroalkenes. The
triazole-containing nitrohydrazones, stable substances,
may be interesting as synthons for the study of cyclo-
addition with various 1,3-dipoles, and also serve as initial
compounds in the synthesis of amidrazones.
3-Methyl-1-(2-methyl-1,2,3-triazol-4-yl)-1-nitro-
2,3-diazabut-1-ene (VII). Yield 43%, mp 78–80°C (from
ethanol). IR spectrum, ν, cm–1: 1550, 1290 (NO2), 1645
(C=N). UV spectrum, λmax, nm (log ε): 235 (4.06), 375
1
(4.07). H NMR spectrum, δ, ppm: 7.26 s (CH), 3.73 s
(CH3), 2.90 s (CH3). Found, %: C 36.21; H 4.92; N 42.27.
C6H10N6O2. Calculated, %: C 36.36; H 5.05; N 42.42.
3-Phenyl-1,2,4-oxadiazole (VIII). Yield 21%, mp
15°C [6].
IR spectra were recorded on a spectrophotometer
IKS -29 from solutions in chloroform of concentration
Compound I was obtained by procedure [5], com-
pounds II–IV, by treatment of the hydrazines hydro-
chlorides with alkali solution followed by extraction into
ethyl ether.
1
40 mg/ml. H NMR spectra were registered on a spec-
trometer Tesla BS-487C (80 MHz) in acetone-d6, internal
reference HMDS. Electron absorption spectra were taken
on a spectrophotometer SF-8 from solutions in ethanol
of concentration 0.4 mg/ml. The homogeneity of com-
pounds obtained was checked and the the reaction
progress was monitored by ascending TLC on Silufol UV-
254 plates in the system acetone–hexane, 2:3, develop-
ment in iodine vapor.
To a solution of 5 mmol of compound I in 15 ml of
anhydrous ethyl ether at 0 ± 5°C was added 5 mmol of
compound II–IV in 50 ml of ether. The reaction mixture
was kept for 2 h at 25°C, evaporated, the residue was
subjected to descending chromatography on a glass
column (250×10 mm) packed with activated Silicagel
100/400μ using Trappe set of eluents. Eluent for
compounds V–VII was benzene, for compound VIII,
ethyl ether.
REFERENCES
1. Tyrkov,A.G., Zh. Org. Khim., 2002, vol. 38, p. 1874.
2. Shvarts, I.M., Krayushkin, M.M., Sevost’yanova, V.V., and
Yarovenko, V.N., Izv. Akad. Nauk SSSR, Ser. Khim., 1979,
p. 813.
3. Manuel’, D.V., Cand. Sci. (Chem.) Dissertation, St. Peters-
burg, 1991.
4. Tyrkov, A.G., Doctoral Sci. (Chem.) Dissertation, Saratov,
2005.
5. Shevtsova, I.A., Tyrkov,A.G., Zh. Org. Khim., 2007, vol. 43,
p. 1740.
1-(2-Methyl-1,2,3-triazol-4-yl)-1-nitro-3,3-di-
phenyl-2,3-diazaprop-1-ene (V). Yield 38%, mp 122–
123°C (from ethanol) [3].
3,3-Dibenzyl-1-(2-methyl-1,2,3-triazol-4-yl)-1-
nitro-2,3-diazaprop-1-ene (VI). Yield 42%, mp 110–
112°C (from ethanol). IR spectrum, ν, cm–1: 1555, 1290
(NO2), 1650 (C=N). UV spectrum, λmax, nm (log ε): 235
1
(l4.12), 372 (4.01). H NMR spectrum, δ, ppm: 7.28 s
(CH), 7.10–7.15 m (Ph), 4.17 s (CH2), 3.77 s (CH3).
Found, %: C 61.58; H 5.03; N 23.78. C18H18N6O2.
Calculated, %: C 61.71; H 5.14; N 24.00.
6. Lenaers, R., Moussebois, C., and Eloy, F., Helv. Shim. Acta,
1962, vol. 45, p. 441.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 45 No. 2 2009