SYNTHESIS OF 3-AZIDO-5-AMINO-1,2,4-TRIAZOLE
583
Yield 0.2 g (5.3%), mp 153 154 C. IR spectrum,
ethyl acetate (2 20 ml). The residue after evapora-
tion of the solvent was added to the main amount of
the product, and the substance was crystallized from
1
cm : 1510, 1570 (cycle), 1630, 1670,1690 (NH2),
1
2175 (N3). H NMR spectrum, , ppm: 7.10 (NH2,
exchange in D2O). Found, %: C 19.42, 19.13; H2.04, dioxane. Yield 25 30%, mp 210 212 C. IR spectrum,
1
2.19; N 78.35, 78.64. C2H3N7. Calculated, %:
C 19.20; H 2.40; N 78.60.
cm : 1525 (cycle), 1640 (NH), 1720 (CO), 2170(N3).
1H NMR spectrum, , ppm: 2.10 (CH3), 11.82 (NH,
exchange in D2O). Found, %: C 29.07, 28.77; H3.18,
2.95; N 58.68, 58.66. C4H5N7O. Calculated, %:
C 28.74; H 2.99; N 58.68.
(b) To 20 ml of 10% HCl was added 1 g
(0.006 mol) of 3-azido-5-acetamido-1,2,4-triazole
(VI), and the mixture was at stirring heated on a
boiling water bath for 5 h. Then the solution was
evaporated to residual volume of 3 5 ml, 5 ml of
ethanol was added, carefully was added sodium
hydrogen carbonate solution till pH 8, and the mix-
ture was transferred into a Petri dish for evaporation
of the solvents, The residue was crystallized from
dioxane. Yield 40%, mp 153 154 C.
3-Azido-5-amino-1-acetyl-1,2,4-triazole
(VII).
Azole III was treated at 0 2 C with a solution of
sodium nitrite as described above, the reaction mix-
ure at cooling was diluted with the same volume of
glacial acetic acid and after addition of a small
amount of urea azidation was carried out by adding
portions of sodium azide solution in double excess
maintaining temperature at 0 2 C. After keeping the
reaction mixture for 0.5 h at this temperature it was
warmed to room temperature, and filtered. The
residue after evaporation of the filtrate was several
times treated with hot ethanol, and the liquid was
decanted through a folded paper filter into a Petri dish
for evaporation. On removing ethanol the residue was
crystallized from 2-propanol. Yield 35 40%, mp
(c) To 10 ml of ethanol was added 1 g (0.006 mol)
of 3-azido-5-amino-1-acyl-1,2,4-triazole (VII),
a
solution of sodium hydrogen carbonate was added till
pH 10, the mixture was heated to 50 C and kept at
that temperature for 10 min, then it was cooled to
0 5 C, acidified to pH 6 7, the separated precipitate
was filtered off and recrystallized. Yield 70%, mp
153 154 C.
1
155 156 C. IR spectrum, cm : 1535 cycle), 1670
1
(d) To 10 ml of 50% sulfuric acid at 10 C was
added at stirring 8.4 g (0.05 mol) of nitrosoguanazole
(V), the mixture was kept for 1 h, 10 ml of cooled
glacial acetic acid was added, and at 5 10 C was
added a solution of 3.9 g (0.06 mol) of sodium azide
in 5 ml of water. The reaction mixture was kept for
0.5 h, then it was transferred into a Petri dish and
evaporated in the cold. Then a solution of sodium
hydrogen carbonate was added till pH 6 7 and
evaporated till dryness. The target product was
extracted with ethanol, the solvent was evaporated,
the residue was crystallized. Yield 40%, mp 153
154 C.
(NH2), 1780 (CO), 2180 (N3). H NMR spectrum, ,
ppm: 2.50 (CH3), 7.35 (NH2, exchange in D2O).
Found, %: C 28.87, 28.64; H 3.04, 2.92; N 58.35,
58.44. C4H5N7O. Calculated, %: C 28.74; H 2.99;
N 58.68.
Azobis(3-azido-1,2,4-triazol-5-yl) (VIII). To a
suspension of 4 g (0.032 mol) of 3-azido-5-amino-
1,2,4-triazole in 25 ml of water was added a solution
of 6 g (0.107 mol) of KOH in 25 ml of water. Then at
stirring was added by portions 4 g (0.025 mol) of
potassium permanganate maintaining the temperature
below 50 C. The reaction mixture was cooled to
room temperature, the separated manganese oxide
was filtered off and washed on the filter with a small
amount of water. The filtrate and washings were
combined, the solution was heated to 70 C, cautious-
ly acidified with glacial acetic acid (minimizing
foaming) till pH 4, the solution was evaporated in a
vacuum till residual volume of 50 60 ml, filtered,
and this filtrate was left standing in a refrigerator for
24 h. The separated precipitate was filtered off and
recrystallized from water. Yield 51%, mp about
3-Azido-5-acetamido-1,2,4-triazole (VI). To a
solution of 3 g (0.021 mol) of 3-amino-5-acetamido-
1,2,4-triazole (IV) in 21.5 ml (0.05 mol) of sulfuric
acid at cooling while stirring was added dropwise a
solution of 1.5 g (0.021 mol) of sodium nitrate in
1.7 ml of water maintaining temperature below 0 2 C.
The reaction mixture was kept at this temperature for
1 h, then a little urea was added, and at 0 2 C was
added by portions a solution of 1.64 g (0.025 mol) of
sodium azide in 13.5 ml of water. The reaction mix-
ture was warmed to room temperature and stirred for
0.5 h. The separated precipitate was filtered off and
washed with water on the filter. To the filtrate a solu-
tion of sodium hydrogen carbonate was added till
pH 5, then the reaction product was extracted into
1
180 C (with ignition). IR spectrum, cm : 1490,
1
1570 (cycle), 2170 (N3). H NMR spectrum, , ppm:
10.10 (NH, exchange in D2O).
Azobis(3-azido-1-methylcarbonylethylyl-1,2,4-
triazol-5-yl) (IX). To a suspension of 3.45 g
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 39 No. 4 2003