Reactions of 3-azido-1,2,4-triazole with electrophiles

Article abstract of DOI:10.1007/s11178-005-0074-5

Alkylation of 3-azido-1,2,4-triazole with oxiranes, bromoacetone, and methyl vinyl ketone furnished a mixture of N-substituted 3- and 5-azido-1,2,4-triazoles, 3-azido compounds prevailing. The same substrate subjected to heterylation with 3,5-dinitro-1,2,4-triazole derivatives reacted selectively at the N¹ atom, and its bromination afforded 3-azido-5-bromo-1,2,4-triazole. 2004 MAIK Nauka/ Interperiodica .

Full text of DOI:10.1007/s11178-005-0074-5

Russian Journal of Organic Chemistry, Vol. 40, No. 11, 2004, pp. 1651 -1656. Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 11,
2004, pp. 1699-1704.
Original Russian Text Copyright Ó 2004 by Kofman, Krasnov.
Reactions of 3-Azido-1,2,4-triazole with Electrophiles
T.P. Kofman and K.N. Krasnov
St. Petersburg State Technological Institute, St. Petersburg, 198013 Russia
fax: (812)112 779
Received December 29, 2003
Abstract-- Alkylation of 3-azido-1,2,4-triazole with oxiranes, bromoacetone, and methyl vinyl ketone furnished a
mixture of N-substituted 3- and 5-azido-1,2,4-triazoles, 3-azido compounds prevailing. The same substrate subjected
to heterylation with 3,5-dinitro-1,2,4-triazole derivatives reacted selectively at the N1 atom, and its bromination
afforded 3-azido-5-bromo-1,2,4-triazole. .
derivatives, and also substrates ensuring functional group
introduction into its N-alkyl fragment. To the latter group
belong oxiranes providing alcohols [II–VI, R = H (II),
CH3 (III), CH2OH (IV), CH2ONO2 (V), CH2Cl (VI)],
and also bromoacetone and methyl vinyl ketone furnishing
the corresponding ketones (VII, VIII) (Scheme 2).
In the 1,2,4-triazole series the reactivity of its azido
derivatives is almost unknown, even that of the first
representative of the series, 3-azido-1,2,4-triazole (I),
although the synthesis [1, 2], electronic structure, vibration
spectra [3], and acid-base properties [4] of 3-azido-5-R-
1,2,4-triazoles has been described some time ago.
The azido derivative I was first synthesized by
nitrozation of 3-hydrazino-1,2,4-triazole [1]. We developed
a simpler method of its preparation in a high yield from
the more available 5-amino-1,2,4-triazole through diazotiza-
tion: by replacing the amino group following the procedure
similar to that described in [2] for the other 3-azido-5-R-
1,2,4-triazoles (Scheme 1).
Scheme 2.
5
1
1
2
1
1
&+ &+ꢀ2+ꢁ5
B
,,DꢀꢁEꢁꢁꢁ9,DꢀꢁE
>2@
Scheme 1.
1
1
1
1
%U&+ &20H
1
1
1
1D12
+
+1
,
1
1
1
&+ &ꢀ2ꢁ0H
1
1
+ 1
9,,DꢀꢁE
1
1
1
+
,
+
+
1
1
+ & &+&20H
1
Compound I is a weak NH-acid (pKa 9.37, 60%
ethanol, 1H NMR [4]; 8.64, water, UV spectroscopy, our
data).
1
&+ &+ &ꢀ2ꢁ0H
9,,,DꢀꢁE
In the series of 3-R-1,2,4-triazoles only the reactivity
of 3-nitro-1,2,4-triazoles is sufficiently well documented.
This compound was studied in reactions of N-alkylation
[5–7], N-addition to unsaturated compounds with an
activated double bond [7], N-heterylation [8], and
halogenation [9]. We attempted to perform analogous
reactions for the 3-azido-1,2,4-triazole using electrophiles
of various characters: bromine, 3,5-dinitro-1,2,4-triazole
3-Nitro-1,2,4-triazole in such syntheses reacts as a
rule at the N1atom, distal with respect to the substituent
in the ring, and does not form appreciable amount of N2-
isomers. The alkylation with a hard electrophile
diazomethane forms an exception, when the N2-isomer
(1-methyl-5-nitro-1,2,4-triazole) attains 24% in the mixture
of N1- and N2-isomers [5]. We found another exception
in reaction with the bromoacetone where the content of
1070-4280/04/4011-1651Ó2004 MAIK “Nauka/Interperiodica”

KOFMAN, KRASNOV.
TLC and 1H NMR data, and the ratio of 3- (IIIa,VIIa,VIIIa) and 5-azido derivatives of 1,2,4-triazole (IIIb,VIIb,VIIIb)
1652
7/&ꢀ
+ꢀ105ꢀVSHFWUXPꢁꢀGꢁꢀSSPꢀ
&RPSGꢂꢀQRꢂꢀ
5DWLRꢀDꢃEꢀ
ꢄꢌꢃꢈꢀ
6ROYHQWꢀV\VWHPꢀ
5 ꢀ
&+ ꢀ
&+ꢀ
&+ ꢀ
& +ꢀ
,,,DꢀꢁEꢁ
$FHWRQH±KH[DQHꢁꢀꢄꢃꢄꢀ
ꢅꢂꢆꢇꢅꢂꢈꢄꢀ
ꢉꢂꢆꢅꢀGꢀ
ꢉꢂꢄꢅꢀGꢀ
ꢆꢂꢊꢅꢀPꢀ
ꢆꢂꢊꢅꢀPꢀ
ꢄꢂꢄꢈꢀGꢀ
ꢄꢂꢄꢈꢀGꢀ
ꢋꢂꢉꢅꢀVꢀ
ꢇꢂꢋꢅꢀVꢀ
9,,DꢀꢁEꢁ +H[DQH±DFHWRQH±(W2$Fꢁꢀ ꢅꢂꢆꢄꢅꢂꢉꢊꢀ
ꢈꢂꢌꢈꢀVꢀ
ꢈꢂꢅꢅꢀVꢀ
±ꢀ
ꢌꢂꢌꢅꢀVꢀ
ꢌꢂꢌꢅꢀVꢀ
ꢋꢂꢉꢅꢀVꢀ
ꢇꢂꢊꢅꢀVꢀ
ꢉꢃꢄꢀ
ꢇꢃꢄꢀ
ꢄꢉꢃꢆꢃꢌꢀ
9,,,DꢀꢁEꢁ +H[DQH±DFHWRQH±(W2$Fꢁꢀ ꢅꢂꢉꢄꢅꢂꢈꢇꢀ ꢉꢂꢆꢌꢀWꢁꢀꢆꢂꢄꢅꢀWꢀ
ꢄꢉꢃꢆꢃꢌꢀ ꢉꢂꢄꢅꢀWꢁꢀꢆꢂꢅꢈꢀWꢀ
±ꢀ
ꢌꢂꢄꢅꢀVꢀ
ꢌꢂꢄꢅꢀVꢀ
ꢋꢂꢌꢌꢀVꢀ
ꢇꢂꢇꢅꢀVꢀ
ꢀ
N2-isomer, 5-nitro-1-(2-oxopropyl)-1,2,4-triazole, in the
reaction products reacted to 5–7% (1H NMR spectros-
copy).
reactions of the 3-azido-1,2,4-triazole with epichloro-
hydrin and nitroglycide respectively.
The alkylation with oxiranes furnished a mixture of
secondary alcohols, 2-hydroxyalkyl derivatives II–VI.
Their structure was proved by oxidation of alcohol III
with chromium(VI) oxide to propanone VII analogous
to the ketone obtained by the direct alkylation of 3-azido-
1,2,4-triazole with bromoacetone. The structures of
N-Alkylation of 3-azido-1,2,4-triazole is not selective
(scheme 2). According to the data of 1H NMR and TLC
(see table) in all cases formed a mixture of N1- and N2-
isomers, the former prevailing. At the same time the
content of the N2-isomer is significant, and it grows in
the series of alkylating agents methyl vinyl ketone -
oxiranes-bromoacetone. The isomers ratio was estimated
from the intensity ratio of the signals of the ring protons
1
alcohols were also confirmed by the H NMR spectra.
In the spectra of all alcohols obtained the chemical shifts
of protons from the CH2 group attached to the heteroatom
had characteristically similar values, both in the spectrum
of the a fortiori primary alcohol II and in the spectra of
all other hydroxy derivatives III–VI. In the spectra of
diols IV the nonequivalence of two methylene groups in
their structure is well seen.
1
(C5H and C3H) whose positions in the H NMR spectrum
was essentially different (Dd 0.5–0.6 ppm). Beside these
signals in the spectra appear the triplets of methylene
group protons from the substituent attached to the
heteroatom of the ring, and the corresponding resonances
of the N1-isomers are located in a weaker field (see
table).
The reactions of the 3-azido-1,2,4-triazole with
bromoacetone and methyl vinyl ketone were performed
by prolonged keeping of the reagents at room temperature
(TLC monitoring). In the first reaction triazole I was
converted into the anion form by sodium hydroxide, in
the second case by triethylamine.
The alkylation of 3-azido-1,2,4-triazole with oxiranes,
same as in reactions with the other triazoles [10], occurs
with regularly increasing pH of the medium caused by
the NH-acid consumption. The accumulation of the target
reaction product proceeds simultaneously and reaches
the maximum yield at pH exceeding the pKa of the
3-azido-1,2,4-triazole by 2.0–2.5 units. Unlike more acidic
substrates (pKa 3–7) the 3-azido-1,2,4-triazole reacts with
epoxides in aqueous ethanol at room temperature at a
considerable rate and without bases, but the addition of
bases significantly accelerates the reaction (adding 1–
10% of the base amount necessary for the total
conversion of the NH-acid into a salt). The use of a larger
quantity of alkali in these syntheses is not required.
Besides the reaction should be stopped in due time: at
pH < 10.5–11. The observance of these conditions
prevents secondary reactions: alkylation of the alcohol
formed with excess epoxy compound and dehydrochlorin-
ation or denitration of alcohols V and VI resulting from
The alkylation products mixtures are as a rule viscous
nondistillable oily substances. However since the N2-
isomers are more soluble in ether, we succeeded in most
cases in separation in a pure state of the prevailing N1-
isomer. To this end the latter was precipitated from the
concentrated ethyl ether solution of the isomer mixture
with petroleum ether (compounds III and VIII) or it was
frozen out from the ether solution (compounds II and
VII), or a fractional crystallization was performed
(compounds IV–VI). The most reach with N2-isomer
propanone VIII was an exception for even after 2–3
reprecipitations it still contained an impurity of this isomer.
In reactions introducing heterocyclic substituents into
the 3-azido-1,2,4-triazole we did not observe any notable
nonselectivity like that found in alkylation. In crude
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 40 No. 11 2004

REACTIONS OF 3-AZIDO-1,2,4-TRIAZOLE WITH ELECTROPHILES
1653
Azole XI possesses relatively high acidity:As estimat-
ed by spectrophotometric procedure, pKa is 1.75 [11].
products of reaction with 3,5-dinitro-1,2,4-triazole
derivatives (R = H, CH2COMe) the N2-isomer was not
revealed by 1H NMR spectroscopy. The reaction mixture
contained only the products of the nitro group replacement
in the substrate: N-C-bitriazoles IXa and Xa and the
corresponding triazole-5-ones IXb and Xb (Scheme 3).
Therewith under standard conditions the overall yield of
the main reaction products was close to quantitative one
[equimolar reagents ratio, medium 90% acetone (two-
phase system ethyl acetate–water), 60 (80)°C, the
reaction mixture stored till complete consumption of the
substrate as shown by TLC]. Note that the NH-acidity
of the 3-arido-1,2,4-triazole falls in the optimal range for
these substitution reactions ensuring both the high yield
of N-C-bitriazoles and the lack of considerable heterolysis
of the initial and bicyclic butanones X under the synthesis
conditions; the latter process is fairly common for this
type compounds [8].
The bromination of the 3-azido-1,2,4-triazole with
bromine along the procedure formerly used with 3-nitro-
1,2,4-triazole [9] gave rise to a bromo derivatives whose
1H NMR spectrum lacked the signal from the proton
C5H.
Scheme 5.
1
1
%U ꢀ1D2+
1
1
,
1
1
%U
1
1
+
%U
;,,
Evidently here like in the other triazoles reactions with
a halogen in an alkaline medium the primary attack is
directed on a heteroatom giving an intermediate N-bromo
derivative that at heating undergoes thermal
intramolecular rearrangement resulting in 3-azido-5-
bromo-1,2,4-triazole (XII) (Scheme 5).
Scheme 3.
12
12
1
1
1
,ꢀꢁ1D2+
1
1
1
1
EXPERIMENTAL
2 1
1
1
1
&+ 5
&+ 5
,;Dꢁꢂ;D
1H NMR spectra were registered on spectrometer
Perkin Elmer R-12 (60 MHz) in acetone-d6, internal
reference HMDS. IR spectra were recorded on
spectrophotometer Specord 75IR (from films). Elemental
analysis was carried out on CHN-analyzer Hewlett-
Packard-185B. Molecular weight was determined by the
method of reversed ebullioscopy in acetone. TLC was
performed on Silufol UV-254 plates.
12
+
1
ꢀ
1
2
1
&+ 5
,;Eꢁꢂ;E
NH-Acidity of biazole XI was measured by spectro-
photometric procedure using a spectrophotometer CF-
16 and a pH-meter pH-262 in aqueous buffer media by a
standard method [11].
R = H (a), CH2COMe (b).
Ketone Xa undergoes hydrolysis in alkaline medium
furnishing a new compound from the bitriazole series, 5-
(3-azido-1,2,4-triazol-1-yl)-3-nitro-1,2,4-triazole (XI)
(Scheme 4).
3-Azido-1,2,4-triazole (I). To a solution of 10 g
(0.12 mol) of 3-amino-1,2,4-triazole in 124 ml (0.288 mol)
of 20% sulfuric acid at a temperature not exceeding 0–
3°C was added dropwise a solution of 8.26 g (0.12 mol)
of sodium nitrite in 10 ml of water. The reaction mixture
was maintained for 30 min at 0°C, to the obtained solution
of the diazonium salt was added a small amount of urea,
and at a temperature not exceeding 0–2°C was added
by portions a solution of 20 g (0.154 mol) of sodium azide
in 80 ml of water. The mixture was kept for 30 min at
18–20°C, the precipitated azido compound I was filtered
off, the filtrate was neutralized with sodium hydrogen
carbonate till pH 5–6 and extracted with ethyl acetate
Scheme 4.
2 1
1
1
1
2 1
ꢀꢁꢂꢃ+2ꢃ
ꢀꢄꢂꢃ+
1
1
1
1
1
1
1
1
1
1
1
&+ &+ &20H
+
;D
;,
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 40 No. 11 2004

KOFMAN, KRASNOV.
1654
(3´50 ml). The combined extracts were washed with
water and dried on calcined magnesium sulfate. The
residue after removing the solvent was added to the
main product, and it was crystallized from toluene. Yield
CH2). Found, %: C 32.85, 32.48; H 4.40, 4.10; N 45.55,
45.94. [M]+ 188. C5H8N6O2. Calculated, %: C 32.88;
H 4.38; N 45.64. M 184.16.
3-Azido-1-(2-hydroxy-3-nitrooxypropyl)-1,2,4-
–1
80%, mp 121–123°C. IR spectrum, n, cm : 980, 1020,
triazole (V). Yield 72%, mp 88–89°C (benzene). IR
1090, 1175, 1260, 1340, 1460, 1515, 2140 (N3). 1H NMR
–1
spectrum, n, cm : 855, 875, 900, 980, 1060, 1070, 1160,
spectrum, d, ppm: 8.40.
3(5)-Azido-N-(2-hydroxyalkyl)-1,2,4-triazoles
(II–VI). To a solution of 2.9 g (0.026 mol) of azidotriazole
1250, 1310, 1360, 1375, 1425, 1550, 1650 (ONO2), 2160
(N3), 3200–3600 (OH). 1H NMR spectrum, d, ppm: 8.40
s (1H, H5), 5.60 s (OH), 4.65 d (2H, CH2), 4.37 d (2H,
I in 15 ml of ethanol placed into a graduated flask of 25 CH2), 4.00 m (1H, CH). Found, %: C 25.97, 25.93;
ml capacity was added a solution of 0.106 g (0.0026 mol)
of sodium hydroxide in 2 ml of water, and 0.046 mol of
epoxide. Then ethanol was added to the 25 ml mark. The
reaction mixture was kept at room temperature in a
stoppered flask measuring intermittently the pH of the
solution (pHinit 7.8). When the pH reached the value of
10.5–11 (48–72 h ) the reaction mixture was diluted with
a double volume of water, and the alcohol formed was
extracted into ethyl acetate (5´50 ml). The extract was
washed with water, dried with calcined magnesium sulfate,
the solvent was removed in a vacuum. 3-Azido-1-(2-
hydroxyalkyl)-1,2,4-triazoles were separated from 5-azido
isomers by freezing out from ether solution (alcohol II),
reprecipitation from ether solution with petroleum ether
(alcohol III), or by fractional crystallization (compounds
IV–VI).
H 3.33, 3.24; N 42.62, 42.77. [M]+ 226. C5H7N7O4.
Calculated, %: C 26.21; H 3.08; N 42.79. M 229.16.
3-Azido-1-(2-hydroxy-3-chloropropyl)-1,2,4-
triazole (VI). Yield 82%, mp 119–120°C (MeOH). IR
–1
spectrum, n, cm : 1050, 1105, 1160, 1190, 1250, 1350,
1360, 1460, 1490, 1540, 2160 (N3), 3400–3600 (OH). 1H
NMR spectrum, d, ppm: 8.40 s (1H, H5), 5.60 (OH),
4.35 d (2H, CH2), 4.00 m (1H, CH), 3.70 d (2H, CH2).
Found, %: C 29.73, 29.85; H 3.19, 3.45; N 41.59, 41.37.
[M]+ 198. C5H7ClN6O. Calculated, %: C 29.89; H 3.48;
N 41.48. M 202.61.
3-Azido-1-(3-oxopropyl)-1,2,4-triazole (VII). (a)
To a solution of 0.07 mol of alcohol III in 190 ml of
acetonea was added by portions while stirring at 25–30°C
a solution of 7 g (0.07 mol) of CrO3 in a diluted sulfuric
acid [preliminary prepared from 14 ml of water and 6.1
ml (0.11 mol) of concn. H2SO4]. The reaction mixture
was stirred for 30 min at 25–30°C, then several drops of
2-propanol was added, the precipitate was filtered off
and washed with acetone. The combined acetone
washings and filtrate were stirred with 10 g of sodium
hydrogen carbonate, the precipitate was filtered off, the
solvent was removed, the residue was dissolved in ether,
the ether solution was washed with water, and dried on
calcined magnesium sulfate. The drying agent was filtered
off, and petroleum ether was added to the solution in
ethyl ether. The arising oily substance was separated,
dissolved in a minimum amount of ether, and the solvent
was removed in a vacuum. Yield 75%, nD2 0 1.5772. IR
3-Azido-1-(2-hydroxyethyl)-1,2,4-triazole (II).
–1
Yield 80%, mp 35–36°C (ether). IR spectrum, n, cm :
870, 950, 1050, 1075, 1130, 1210, 1250, 1280, 1355, 1380,
1435, 1495, 1540 (cycle), 2170 (N3), 3200–3600 (OH).
1H NMR spectrum, d, ppm: 8.40 s (1H, H5), 5.60 t (1H,
OH), 4.30 t (2H, CH2), 3.97 t (2H, CH2). Found, %: C
30.88, 31.31; H 3.51, 3.42; N 54.94, 54.32. [M]+ 153.
C4H6N6O. Calculated, %: C 31.12; H 3.92; N 54.53. M
154.13.
3-Azido-1-(2-hydroxypropyl)-1,2,4-triazole (III).
20
–1
Yield 85%, nD 1.5253. IR spectrum, n, cm : 860, 950,
1060, 1090, 1150, 1200, 1250, 1280, 1290, 1350, 1390,
1450, 1480, 1530 (cycle), 2170 (N3), 3200–3600 (OH).
1H NMR spectrum, d, ppm: 8.40 s (1H, H5), 5.00 (1H,
OH), 4.30 d (2H, CH2), 3.90 m (1H, CH), 1.15 d (3H,
CH3). Found, %: C 35.72, 35.47; H 5.15, 5.29; N 49.54,
49.28. [M]+ 164. C5H8N6O. Calculated, %: C 35.71; H
4.80; N 49.98. M 168.16.
–1
spectrum, n, cm : 1040, 1070, 1170, 1185, 1230, 1340,
1375, 1435, 1460, 1530, 1725 (C=O), 2140 (N3). 1H NMR
spectrum, d, ppm: 8.40 s (1H, H5), 5.25 s (2H, CH2),
2.20 s (3H, CH3). Found, %: C 36.49, 36.23; H 3.55,
3.62; N 51.01, 50.77. [M]+ 170. C5H6N6O. Calculated,
%: C 36.15; H 3.64; N 50.62. M 166.14.
3-Azido-1-(2,3-dihydroxypropyl)-1,2,4-triazole
(IV). Yield 75%, mp 77–78°C (MeOH). IR spectrum, n,
–1
(b) To a solution of 5 g of azole I in 20 ml of ethanol
was added at room temperature while stirring a solution
of 1.84 g of sodium hydroxide in 3 ml of water, and 7 ml
of bromoacetone. The reaction mixture was left standing
cm : 870, 940, 960, 980, 1040, 1060, 1090, 1160, 1210,
1250, 1365, 1460, 1540 (cycle), 2170 (N3), 3200–3600
(OH). 1H NMR spectrum, d, ppm: 8.35 s (1H, H5), 4.90
s (OH), 4.51 d (2H, CH2), 4.29 m (1H, CH), 3.97 d (2H,
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 40 No. 11 2004

REACTIONS OF 3-AZIDO-1,2,4-TRIAZOLE WITH ELECTROPHILES
1655
for 5 days. The solvent then was removed, the residue
was dissolved in ether, the solution was washed with
water, and dried on calcined magnesium sulfate. The
solvent was removed in a vacuum, the oily residue
(isomer mixture) was dissolved in a minimum amount of
ether, and petroleum ether was added thereto. The
precipitated product was separated, and the reprecipitation
was repeated 2–3 times, yield 40% (impurity of N2-isomer,
TLC).
4.30 (3H, CH3). Found, %: C 25.73, 25.50; H 1.81, 1.72;
N 59.72, 59.81. [M]+ 230. C5H4N10O2. Calculated, %: C
25.64; H 1.83; N 59.31. M 236.16.
5-(3-Azido-1,2,4-triazol-1-yl)-3-nitro-1,2,4-
triazole-1-butan-3-one (Xa). Yield 65%, mp 79–80°C
(aqueous EtOH). 1H NMR spectrum, d, ppm: 9.13 s (1H,
H5), 4.81 t (2H, CH2), 3.25 t (2H, CH2 ), 2.15 s (3H,
–1
CH3). IR spectrum, n, cm : 1340, 1360, 1425, 1480, 1540
(bicycle), 1600 (bicycle), 1750 (C=O), 2175 (N3). Found,
%: C 32.96, 32.81; H 2.90, 2.99; N 48.45, 48.07. [M]+
301. C8H8N10O3. Calculated, %: C 33.15; H 2.76;
N 47.93. M 292.22.
3-Azido-1-(3-oxobutyl)-1,2,4-triazole (VIII). To a
solution of 0.044 mol of triazole I in 15 ml of ethanol was
added 1 ml of triethylamine and 4.5 ml (0.054 mol) of
methyl vinyl ketone. The reaction mixture was kept for
48 h at room temperature, the solvent was removed, and
the residue was crystallized from ether by cooling the
concentrated ether solution to –30...–40°C. Yield 65%,
5-(3-Azido-1,2,4-triazol-1-yl)-3-nitro-1,2,4-
triazole (XI). To a solution of 0.48 g (0.12 mol) of sodium
hydroxide in 25 ml of water was added at cooling while
stirring 0.04 mol of butanone Xa, the reaction mixture
was left standing at 18–20°C till it turned homogeneous,
the mixture was extracted with ether (25 ml) to remove
the formed methyl vinyl ketone, the water layer was
acidified with 10% sulfuric acid till pH 1, and extracted
with ethyl acetate (3´25 ml). The extract was washed
with water, the solvent was removed, and the residue
was crystallized. Yield 72%, mp 154–155°C (chloroform).
–1
mp 34–35OC (ether). IR spectrum, n, cm : 1040, 1070,
1170, 1185, 1230, 1340, 1375, 1435, 1460, 1530, 1725
1
(C=O), 2140 (N3). H NMR spectrum, d, ppm: 8.22 s
(1H, H5), 4.32 t (2H, CH2), 3.10 t (2H, CH2), 2.15 s (3H,
CH3). Found, %: C 39.86, 40.18; H 4.59, 4.74; N 46.90,
46.58. [M]+ 177. C6H8N6O. Calculated, %: C 40.00;
H 4.48; N 46.65. M 180.17.
–1
IR spectrum, n, cm : 850, 970, 1050, 1205, 1312, 1335,
1-R-Methyl-3-nitro-5-(3-azido-1,2,4-triazol-1-yl)-
1,2,4-triazoles (IXa, Xa). To a preliminary prepared
solution of 0.03 mol of azidotriazole I in 5 ml of water
containing 0.03 mol of sodium hydroxide was added at
room temperature while stirring a solution of 0.025 mol
of 1-RCH2-3,5-dinitro-1,2,4-triazole (R = H, CH2COMe)
[5, 7] in 45 ml of acetone (ethyl acetate). The reaction
mixture was heated at reflux till complete consumption
of the substarate [TLC monitoring, solvent system:
hexane–acetone–ethyl acetate, 5:2:1; Rf of susbtrates:
0.58 (R = Me), 0.56 (R = CH2COMe)]. The solvent was
evaporated, 20 ml of water was added to the residue, the
mixture was stirred for 20 min, the insoluble part (bi-
triazole) was filtered off, washed with water on the filter,
dried, and crystallized. The combined filtrates and wash
water were acidified with 10% sulfuric acid to pH 1,
extracted with ethyl acetate (3´25 ml), the extract was
washed with water, and dried with calcined magnesium
sulfate, the solvent was removed, and the residue (the
corresponding triazolones IXb, Xb) were crystallized.
Triazolones IXb and Xb were identical to compounds
we had described before [8].
1465, 1515, 1532, 1565, 1605, 2155 (N3). 1H NMR
spectrum, d, ppm: 9.20 s (H5). Found, %: C 21.20, 21.55;
H 0.78, 0.81; N 62.75, 62.80. [M]+ 226. C4H2N10O2.
Calculated, %: C 21.63; H 0.91; N 63.10. M 222.13.
3-Azido-5-bromo-1,2,4-triazole (XII). A mixture of
1.08 g (0.027 mol) of NaOH in 20 ml of water, 3 g
(0.027 mol) of azole I, and 1.5 ml of bromine was
cautiously heated to boiling and maintained on the boiling
water bath for 20 h, then it was cooled, acidified with
20% sulfuric acid till pH 3, and extracted with ether (3´30
ml). The extract was washed with water, dried with
calcined magnesium sulfate, the solvent was removed,
and the residue was crystallized. Yield 60%, mp 64–65°C
–1
(hexane). IR spectrum, n, cm : 995, 1030, 1140, 1235,
1255, 1330, 1425, 1480, 1530, 2145 (N3). Found, %:
C 12.52, 12.87; H 0.72, 0.81; N 44.92, 44.71. [M]+ 198.
C2HBrN6. Calculated, %: C 12.71; H 0.53; N 44.47. M
188.98.
The study was carried out under financial support of
the International Science and Technology Center
(project 2468).
5-(3-Azido-1,2,4-triazole-1-yl)-1-methyl-3-nitro-
REFERENCES
1,2,4-triazole (IXa). Yield 75%, mp 125–126°C (EtOH).
–1
IR spectrum, n, cm : 850, 900, 980, 1190, 1320, 1340,
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RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 40 No. 11 2004

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