Synthesis and study of thermal stability of 3-nitro-1,2,4-triazole N-nitroxy- and N-azidomethyl derivatives

Article abstract of DOI:10.1007/s11172-009-0327-5

A method for the preparation of new 3-nitro-1,2,4-triazole derivatives has been suggested based on modification of the N-hydroxymethyl group by nitration and nucleophilic substitution reactions. Thermal stability of 3-nitro-1,2,4-triazole N-nitroxy- and N

Full text of DOI:10.1007/s11172-009-0327-5

Russian Chemical Bulletin, International Edition, Vol. 58, No. 11, pp. 2356—2361, November, 2009
2356
Synthesis and study of thermal stability of 3ꢀnitroꢀ1,2,4ꢀtriazole
Nꢀnitroxyꢀ and Nꢀazidomethyl derivatives*
I. V. Tselinskii, V. V. Tolstyakov, S. M. Putis, and S. F. Mel´nikova
St.ꢀPetersburg State Institute of Technology,
26 Moskovskii prosp., 190013 St.ꢀPetersburg, Russian Federation.
Eꢀmail: ivts@ltiꢀgti.ru
A method for the preparation of new 3ꢀnitroꢀ1,2,4ꢀtriazole derivatives has been suggested
based on modification of the Nꢀhydroxymethyl group by nitration and nucleophilic substitution
reactions. Thermal stability of 3ꢀnitroꢀ1,2,4ꢀtriazole Nꢀnitroxyꢀ and Nꢀazidomethyl derivaꢀ
tives, as well as of dinitrates, 5,5´ꢀdinitroꢀ2,2´ꢀbisnitroxymethylꢀ2H,2´Hꢀ3,3´ꢀbi(1,2,4ꢀtriazole)
and ꢀ(nitromethylene)bis(1,2,4ꢀtriazole), has been studied.
Key words: 1,2,4ꢀtriazole, 3ꢀnitroꢀ1,2,4ꢀtriazole, dinitromethane, hydroxymethylation,
nitration, nitrates, nucleophilic substitution, azidomethylation, thermal stability.
A possibility of preparation of 3ꢀnitroꢀ1,2,4ꢀtriazole
1ꢀnitroxymethyl and 1ꢀazidomethyl derivatives has been
studied in the present work. Such compounds can be of
interest as energyꢀrich materials used in pyrotechnic
compositions of safety systems,1,2 as well as they
can serve as intermediates in the synthesis of other
3ꢀnitroꢀ1,2,4ꢀtriazole derivatives.3 A combination of
3ꢀnitroꢀ1,2,4ꢀtriazole heterocycle and nitroxymethyl
or azidomethyl groups has not been earlier studied.
* Dedicated to the memory of Corresponding Member of the
Academy of Sciences of the USSR S. S. Novikov on the occaꢀ
sion of his 100th anniversary.
Scheme 1
6, 7: Z = (CH2)n, n = 0 (a), 1 (b), 2 (c);
8: Z = (CH2)n, n = 0 (a), 2 (b)
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2283—2287, November, 2009.
1066ꢀ5285/09/5811ꢀ2356 © 2009 Springer Science+Business Media, Inc.

Derivatives of 3ꢀnitroꢀ1,2,4ꢀtriazole
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 11, November, 2009 2357
The synthesis of such compounds included preparaꢀ
tion of 3ꢀnitroꢀ1,2,4ꢀtriazole 1ꢀhydroxymethyl derivatives,
nitration or tosylation of the hydroxy group and nucleoꢀ
philic replacement of the nitroxy and tosylate groups by
the azide anion (Scheme 1).
The reactivity and thermodynamic properties of
3ꢀnitroꢀ1,2,4ꢀtriazole Nꢀhydroxymethyl derivatives have
been studied earlier.4,5 Some specific features in behavior
of such compounds were found, in particular, lability of
the hydroxymethyl group in the halogenation and acylꢀ
ation reactions. At the same time, conditions for successꢀ
ful performing these reactions were selected,4 as well as
tosyloxymethyl derivatives were obtained.
1319) and nitroxy groups (ν/cm–1: 1693, 1240). Comꢀ
pound 9 slowly decomposes in air at room temperature
with evolution of nitrogen oxides. Nitration of compound
6b unsubstituted at the nitrogen atom heterocycle, also
proceeds at the methylene group. In this case, nitration
with the mixture of sulfuric and nitric acids leads to
the formation and isolation of mononitro derivative
10, whereas under more drastic conditions, unstable
gemꢀdinitro derivative 11 was obtained, which hydrolyzes
in water at 25 °C to ketone 12 (Scheme 2). These results
agree with the reported data,7 which, however, contain no
reaction conditions.
We suggested that it would be simple enough to synꢀ
thesize triazole Nꢀazidomethyl derivatives by tosylation
of the hydroxy group with subsequent nucleophilic substiꢀ
tution of the tosylate group for the azide anion. However,
it turned out that such a way of transformation can be
recommended only for compound 4. The activities of
bisꢀtriazole 1ꢀtosyloxymethyl derivatives proved so high
that the reaction products could not be even isolated from
the reaction mixture: only unsubstituted at position 1 bisꢀ
nitrotriazoles 6a—c were obtained instead of expected
tosylates. Compound 4 was synthesized according to the
procedure described earlier4 with modifications to avoid
rapid decomposition of the products obtained: the reacꢀ
tion time was reduced to 0.5 h and the isolation was
performed by pouring the reaction mixture onto ice, rather
than into aqueous hydrochloric acid, with subsequent
cooling and careful acidification with hydrochloric acid
to neutrality. Nucleophilic substitution for the azide
anion in compound 4 takes place in DMF with sodium
azide in the presence of catalytic amount of benzylꢀ
triethylammonium chloride for 5—8 h at 20 °C without
any complications.
1ꢀHydroxymethylꢀ3ꢀnitroꢀ1Hꢀ1,2,4ꢀtriazoles 2 and
7a—c were synthesized using an improved procedure4 by
the reaction of the starting compounds 1 and 6a—c with
formaline in aqueous or ethanol solution. When the nitraꢀ
tion is carried out in concentrated nitric acid, the starting
compounds do not react, whereas in the mixture of sulfuꢀ
ric and nitric acids, the N—CH2OH bond is cleaved to
yield triazoles unsubstituted at position 1. Hydroxymethyl
compounds 2 and 7a—c were nitrated in the conc. nitric
acid—acetic anhydride system at 0 °C similarly to the
procedure suggested earlier6 for the synthesis of close in
structure and chemical properties (5ꢀnitroꢀ2Hꢀtetrazolꢀ
2ꢀyl)methyl nitrate. The reaction results in obtaining
expected derivatives 3 and 8a,b, whereas in the case of
compound 7b, the nitration also occurred at the methylꢀ
ene group and led to nitromethylene derivative 9. The
1H NMR spectrum of compound 9 exhibits a signal at
δH 7.2 characteristic of the C—H proton together with
two signals at δH 6.92 and 6.80 assigned to the CH2 proꢀ
tons. The nonequivalence of the proton in the CH2 groups
is explained by the steric strain of the molecules and
different spatial interaction of the nitroxymethyl group
with the nitro group at the "bridged" carbon atom, which
results in the molecule to acquire properties of the chiral
nonequivalence.
As to the rest of compounds of the nitrotriazole series
studied, we attempted to involve 1ꢀnitroxymethyl derivaꢀ
tives into this reaction in order to synthesize 1ꢀazidomethyl
derivatives. Substitution of the nitroxy group for the azide
anion, similarly to tosylates, was performed in DMF at
room temperature over a long period of time, however,
The IR spectrum exhibits absorption bands of the
stretching vibrations for both the nitroꢀ (ν/cm–1: 1566,
Scheme 2
i. HNO3, dilute H2SO4; ii. HNO3, conc. H2SO4.

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Russ.Chem.Bull., Int.Ed., Vol. 58, No. 11, November, 2009
Tselinskii et al.
T/°С
T
T/°С
T
b
a
250
200
200
150
100
50
DTA
150
100
DTA
50
0
10
20
30
40
50
60 τ/min
10
20
30
40
50
60
τ/min
m/mg
m/mg
0
5
5
10
15
10
15
TG
TG
60
10
20
30
40
50
T
τ/min
10
20
30
40
50
60 τ/min
T/°С
T/°С
c
d
250
250
DTA
DTA
200
150
T
200
150
100
50
100
50
10
20
30
40
50
60
τ/min
10
20
30
40
50
60
τ/min
m/mg
m/mg
0
5
5
10
15
TG
10
15
TG
60
10
20
30
40
50
60
τ/min
10
20
30
40
50
τ/min
Fig. 1. Thermogravimetric (TG), temperature (T), and thermal differential (DTA) curves of (3ꢀnitroꢀ1Hꢀ1,2,4ꢀtriazolꢀ1ꢀyl)methyl
nitrate (3) (a), 1ꢀ(azidomethyl)ꢀ3ꢀnitroꢀ1Hꢀ1,2,4ꢀtriazole (5) (b), 5,5´ꢀdinitroꢀ2,2´ꢀdi(nitroxymethyl)ꢀ2H,2´Hꢀ3,3´ꢀbi(1,2,4ꢀtriazole)
(8a) (c), 5,5´ꢀdinitroꢀ2,2´ꢀdi(nitroxymethyl)ꢀ2H,2´Hꢀ3,3´ꢀ(nitromethylene)bis(1Hꢀ1,2,4ꢀtriazole) (9) (d).

Derivatives of 3ꢀnitroꢀ1,2,4ꢀtriazole
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 11, November, 2009 2359
we succeeded only in obtaining compound 5. In the case
of bisꢀtriazole derivatives 8a,b involved into this reaction,
the N—CH2ONO2 bond was found to be extremely
unstable and only sodium salts 6a and 6c were isolated as
the reaction products.
stability and are prospective for further study in the field
of pyrotechnic composition applications.
Experimental
For the most energyꢀrich from the point of view of
oxygen balance compounds 3, 5, 8a, and 9, studies
of their thermal stability have been carried out, since it
is the most important physicoꢀchemical characteristic
governing their practical use. Derivatographic analysis
includes thermographic and thermogravimetric studies
of compounds in the regime of programmed heating. The
temperature curve T in Fig. 1 corresponds to the sample
temperature, the TG curve, to the sample mass change
with time, the DTA curve, to the temperature difference
between the sample and the standard (it allows one to
make qualitative and quantitative evaluation of physicoꢀ
chemical processes). Thus, the direction of the peak
deviation on the DTA curve determines character of the
thermal effect (endoꢀ or exothermic, the lower and upper
peaks, respectively). The peak area on the DTA curve is
proportional to the enthalpy effect. To make conclusions
on physicoꢀchemical transformations taking place in the
sample, we performed coꢀanalysis of the TG and DTA
curves with orientation in coordinates by the T curve.8
As the thermal differential analysis data show, comꢀ
pound 3 is stable enough in the liquid state, virtually
involatile to the decomposition onset (t = 0—38 min) and
intensively decomposes at the temperatures above 150 °C,
which is characteristic of compounds containing nitroxy
group. On the contrary, azidomethyl derivative 5 is
somewhat volatile starting from 20 °C and loses ∼7 wt.%
to the melting onset (50 °C, the peak at t = 16—18 min),
the mass loss reaches already ∼50% to the moment of
decomposition onset. It is necessary to note that the temꢀ
perature of intensive decomposition onset for compound
5 is 175—180 °C, which is higher than that for nitroxy
derivative 3.
Compound 8a begins to slowly decompose before
melting (at ∼130 °C). The decomposition proceeds in two
steps, the first step begins to be visible at 160 °C (with
melting), whereas intensive decomposition starts at
187 °C, the second step begins at 210 °C, the peak
is observed at 230 °C. Judging from the mass loss, the
N—CH2ONO2 bond cleavage occurs in the first step (the
mass loss is 40—45%), the rest of the molecules decomꢀ
pose in the second step. It is quite difficult to interpret
thermal decomposition of compound 9, though, the
general picture of decomposition is similar to that for
8a. Both compounds decompose in two steps, whereas
the presence of the nitromethylene bridge in compound 9
causes the melting point and the intensive decomposition
onset temperature to decrease by ∼60 °C.
1H and 13C NMR spectra were recorded on a Bruker
DPXꢀ300 (300 MHz) and Bruker AMꢀ200 (200 MHz) specꢀ
trometers using residual signals of the solvent (DMSOꢀd6, δ 2.50)
as the reference. IR spectra were recorded on a Perkin—Elmer
Spectrum 1000 spectrometer in KBr pellets. Elemental analysis
was performed on a Hewlett—Packard 185, C,H,NꢀAnalyser
automatic instrument. Melting points were determined on a
PTP instrument at the rate of heating of 1 °C min–1 in the
melting interval. The reaction progress was monitored by TLC on
Merck Kieselgel 60F245 plates with visualization by the UV light.
Compounds 3, 5, 8a, and 9 were analyzed on a F. Paulik,
J. Paulik, L. Erdey derivatograph under the following conditions:
the nonisothermic regime, the temperature range of 20—500 °C,
the rate of heating of 5 °C min–1, air as the medium, a quartz
crucible. The weights of the compounds 3, 5, 8a, and 9 samples
were 20, 20, 11, and 20 mg, respectively. Compounds 5 and 9
were diluted with the inert compound Al2O3 (dilution of 1 : 10),
compound 8a with Al2O3, (1 : 50). The starting compounds 1
and 6a—c were synthesized according to the procedure described
earlier.9
(3ꢀNitroꢀ1Hꢀ1,2,4ꢀtriazolꢀ1ꢀyl)methanol (2). Formaline
(30% aq. solution, 10 mL) was added to 3ꢀnitroꢀ1Hꢀ1,2,4ꢀ
triazole (1) (1.44 g, 0.01 mol) in water (100 mL). The reaction
mixture was stirred for 16 h at 20—25 °C, then it was placed into
a refrigerator. A precipitate formed was filtered off, washed with
water (3Ѕ20 mL), and dried in air. Crystallization from chloroꢀ
form yielded product 2 (11.2 g, 78%), m.p. 80—81 °C (cf. Ref. 4:
m.p. 80—81 °C). 1H NMR, δ: 8.75 (s, 1 H, C(5)H); 7.30 (s, 1 H,
OH); 5.55 (s, 2 H, CH2). IR, ν/cm–1: 3352, 3161, 2341, 1558,
1515, 1417, 1311, 1220, 1186, 1107, 1053, 1012, 875, 840.
Found (%): C, 24.9; H, 2.5; N, 39.0. C3H4N4O3. Calculꢀ
ated (%): C, 25.0; H, 2.8; N, 38.9.
[5,5´ꢀDinitroꢀ2H,2´Hꢀ3,3´bi(1,2,4ꢀtriazole)ꢀ2,2´ꢀdiyl]ꢀ
dimethanol (7a). For the synthesis of this product, compound 6a
(0.01 mol) and 30% aq. formaline (20 mL) were used, with
ethanol as the solvent; the reaction and isolation conditions
were similar to those described for compound 2. The yield was
2.11 g (70%), m.p. 179 °C. 1H NMR, δ: 6.05 (s, 2 H, OH); 6.00
(s, 4 H, CH2). IR, ν/cm–1: 3230, 1560, 1520, 1490, 1400, 1380,
1310, 1220, 1150, 850. Found (%): C, 25.2; H, 2.1; N, 39.0.
C6H6N8O6. Calculated (%): C, 25.2; H, 2.1; N, 39.2.
[5,5´ꢀMethylenebis(3ꢀnitroꢀ1Hꢀ1,2,4ꢀtriazole)ꢀ1,1´ꢀdiyl]ꢀ
dimethanol (7b). For the synthesis of this product, compound 6b
(0.01 mol) and 30% aq. formaline (20 mL) were used with
ethanol as the solvent; the reaction and isolation conditions
were similar to those described for compound 2. The yield was
2.64 g (88%), m.p. 154—155 °C. 1H NMR, δ: 4.09 (s, 2 H,
CH2); 5.63 (s, 4 H, CH2); 5.67 (s, 2 H, OH). IR, ν/cm–1: 3120,
3000, 2966, 1560, 1520, 1400, 1310, 1270, 1200, 1040, 970.
Found (%): C, 28.1; H, 2.5; N, 37.1. C7H8N8O6. Calculꢀ
ated (%): C, 28.0; H, 2.7; N, 37.3.
[5,5´ꢀ(1,2ꢀEthylene)bis(3ꢀnitroꢀ1Hꢀ1,2,4ꢀtriazoleꢀ1,1´ꢀdiyl]ꢀ
dimethanol (7c). For the synthesis of this product, compound 6c
(0.01 mol) and 30% aq. formaline (20 mL) were used with
ethanol as the solvent; the reaction and isolation conditions
In conclusion, 3ꢀnitroꢀ1,2,4ꢀtriazole 1ꢀnitroxymethyl
and 1ꢀazidomethyl derivatives have rather high thermal

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Russ.Chem.Bull., Int.Ed., Vol. 58, No. 11, November, 2009
Tselinskii et al.
were similar to those described earlier for compound 2. The
in DMF (30 mL) with the additive of benzyltriethylammonium
chloride (0.1 g) was stirred for 8 h at ∼20 °C. The reaction course
was monitored by TLC. Then the reaction mixture poured into
water (200 mL) and extracted with ethyl acetate (4×30 mL). The
extract was dried with MgSO4 and concentrated in a Petri dish
in vacuo. The oily residue was placed into a freezer (temperature
–20 °C) for 5—6 h. Diethyl ether (5—6 mL) was added to the
crystalline product formed, which was filtered off and washed
on the filter with diethyl ether (1—2 mL). The yield was 1.2 g
1
yield was 2.70 g (80%), m.p. 186 °C. H NMR, δ: 7.50 (s, 2 H,
OH); 5.60 (s, 2 H, CH2); 3.45 (s, 4 H, CH2). IR, ν/cm–1
:
3248, 3000, 2974, 1523, 1558, 1423, 1315, 1134, 1087, 852.
Found (%): C, 30.4; H, 3.2; N, 35.6. C8H10N8O6. Calculꢀ
ated (%): C, 30.6; H, 3.2; N, 35.7.
Synthesis of 3ꢀsubstituted 1ꢀnitroxymethyl 1Hꢀ1,2,4ꢀtriazoles
(general procedure). Hydroxymethyl derivative 2 (0.025 mol)
or hydroxymethyl derivative 7a—c (0.0125 mol) was added
with stirring to the mixture consisting of 97% aq. nitric acid
(40 mL) and acetic anhydride (40 mL) at temperatures no
higher than 0 °C. The reaction mixture was stirred at this
temperature for 5 h, then poured onto finely crashed ice
(200 g). A solution obtained was carefully neutralized with 10%
aq. sodium bicarbonate to рH 4—5. A precipitate formed
(for 7a—c) was filtered off, washed with water to neutrality,
and dried in air or (for 2) extracted with ethyl acetate
(3×50 mL), ethyl acetate was evaporated in air, and then the
residue was dried for 12 h in vacuumꢀdessicator over phosphorus
pentoxide.
1
(71%), m.p. 51—52 °C. H NMR, δ: 5.81 (s, 2 H, CH2); 9.0 (s,
1 H, C(5)H). IR, ν/cm–1: 3128, 2165, 2123, 1560, 1548, 1512,
1452, 1433, 1407, 1382, 1363, 1298, 1244, 1197, 1122, 1043,
1029, 1010, 916, 861. Found (%): C, 20.9; H, 1.9; N, 58.0.
C3H3N7O2. Calculated (%): C, 21.3; H, 1.8; N, 58.0.
5,5´ꢀ(Nitromethylene)bis(3ꢀnitroꢀ1Hꢀ1,2,4ꢀtriazole) (10).
Compound 6b (1.2 g, 0.005 mol) was added to a nitrating mixture
consisting of 65% aq. nitric acid (7 mL) and 94% sulfuric acid
(11 mL) at 0—5 °C. The reaction mixture was stirred for 8 h
at 20—25 °C, then poured onto finely crashed ice (70 g), and
extracted with ethyl acetate (5×30 mL). The organic layer was
washed with water and dried with anhydrous MgSO4. Ethyl
acetate was evaporated in the flow of air, the residue was
recrystallized from chloroform—carbon tetrachloride mixture.
The yield was 0.59 g (42%), m.p. 118 °C (cf. Ref. 7: m.p. 118 °C).
1H NMR, δ: 10.05 (br.s, 2 H, NH); 7.10 (s, 1 H, CH). IR,
ν/cm–1: 3100, 3010, 2966, 1556, 1430, 1323, 1250, 1050, 960.
Found (%): C, 21.1; H, 1.0; N, 44.7. C5H3N9O6. Calculꢀ
ated (%): C, 21.2; H, 1.1; N, 44.5.
Dinitrobis(3ꢀnitroꢀ1Hꢀ1,2,4ꢀtriazoleꢀ5ꢀyl)methane (11).
Compound 6b (1.2 g, 0.005 mol) was added to a nitrating mixture
consisting of 96% nitric acid (7 mL) and 99.5% sulfuric acid
(11 mL) at 0—5 °C. The reaction mixture was stirred for 8 h
at 20—25 °C, then poured onto finely crashed ice (70 g), and
extracted with ethyl acetate (5×30 mL). The organic layer was
washed with water and dried with anhydrous MgSO4. Ethyl
acetate was evaporated in the flow of air. The yield was 0.93 g
(57%), m.p. 52 °C (with decomp.). 1H NMR, δ: 10.68 (br.s,
2 H, NH). IR, ν/cm–1: 1565, 1510, 1420, 1315, 1248, 1210,
1070, 950. Found (%): C, 19.5; H, 0.5; N, 43.0. C5H2N10O8.
Calculated (%): C, 19.3; H, 0.6; N, 42.7.
(3ꢀNitroꢀ1Hꢀ1,2,4ꢀtriazolꢀ1ꢀyl)methyl nitrate (3). Crysꢀ
tallization from diethyl ether yielded compound 3 (2.7 g, 50%),
1
m.p. 104—105 °C. H NMR, δ: 9.05 (s, 1 H, C(5)H); 6.75 (s,
2 H, CH2). Found (%): C, 19.4; H, 1.8; N, 36.6. C3H3N5O5.
Calculated (%): C, 19.1; H, 1.6; N, 37.0.
5,5´ꢀDinitroꢀ2,2´ꢀdi(nitroxymethyl)ꢀ2H,2´Hꢀ3,3´ꢀbi(1,2,4ꢀ
triazole) (8a). The yield was 2.70 g (72%), m.p. 163 °C.
1H NMR, δ: 7.04 (s, 4 H, CH2). IR, ν/cm–1: 3062, 2997, 1685,
1558, 1481, 1454, 1319, 1280, 983. Found (%): C, 19.4; H, 1.2;
N, 37.2. C6H4N10O10. Calculated (%): C, 19.2; H, 1.1; N, 37.2.
5,5´ꢀDinitroꢀ2,2´ꢀdi(nitroxymethyl)ꢀ2H,2´Hꢀ3,3´ꢀ(nitroꢀ
methylene)bis(1,2,4ꢀtriazole) (9). The yield was 2.0 g (27.5%),
m.p. 108—109 °C. 1H NMR, δ: 7.20 (s, 1 H, CH); 6.92 (s, 2 H,
CH2); 6.80 (s, 2 H, CH2). IR, ν/cm–1: 3005, 2995, 1693, 1566,
1575, 1438, 1319, 1240, 1234, 1072, 968. Found (%): C, 19.2;
H, 1.2; N, 35.6. C7H5N11O12. Calculated (%): C, 19.3; H, 1.2;
N, 35.4.
5,5´ꢀDinitroꢀ2,2´ꢀdi(nitroxymethyl)ꢀ2H,2´Hꢀ3,3´ꢀethyleneꢀ
bis(1,2,4ꢀtriazole) (8b). The yield was 1.25 g (90%), m.p. 174 °C.
1H NMR, δ: 6.80 (s, 4 H, CH2); 3.65 (s, 4 H, CH2). IR, ν/cm–1
:
3051, 2982, 1678, 1566, 1523, 1423, 1134, 1049, 991, 856.
Found (%): C, 24.0; H, 1.8; N, 34.9. C8H8N10O10. Calculꢀ
ated (%): C, 23.8; H, 2.0; N, 34.7.
Bis(3ꢀnitroꢀ1Hꢀ1,2,4ꢀtriazoleꢀ5ꢀyl)methanone (12). Freshly
obtained compound 11 (0.82 g, 0.0025 mol) was added to water
(50 mL) at 20—25 °C. The reaction mixture was stirred for 5 h at
the temperature indicated, then extracted with ethyl acetate
(5×20 mL). The organic layer was dried with anhydrous MgSO4.
Ethyl acetate was evaporated in the flow of air, the residue was
recrystallized from methanol—chloroform. The yield was 0.47 g
(75%), m.p. 175 °C (cf. Ref. 7: m.p. 175 °C). 1H NMR, δ: 10.00
(br.s, 2 H, NH). 13C NMR, δ: 173.8 (C=O); 156.6 (C(3)—NO2);
147.2 (C(5)—C=O). IR, ν/cm–1: 1680, 1540, 1410, 1320, 1230,
1110, 1040, 980. Found (%): C, 23.9; H, 0.7; N, 44.3. C5H2N8O5.
Calculated (%): C, 23.8; H, 0.8; N, 44.4.
(3ꢀNitroꢀ1Hꢀ1,2,4ꢀtriazolꢀ1ꢀyl)methyl 4ꢀmethylbenzeneꢀ
sulfonate (4). Freshly recrystallized pꢀtoluenesulfonyl chloride
(98.04 g, 0.042 mol) was added to a solution of (3ꢀnitroꢀ1Hꢀ
1,2,4ꢀtriazolꢀ1ꢀyl)methanol (2) (6 g, 0.042 mol) in anhydrous
pyridine (20 mL) at –5—0 °C. The reaction mixture was stirred
for 0.5 h at 0 °C and poured onto finely crushed ice (50 g). The
mixture obtained was carefully neutralized with 10% aq. hydroꢀ
chloric acid (∼150 mL), a precipitate formed was filtered off,
washed with water, dried, and recrystallized from acetone—
ethanol solvent mixture (1 : 1). The yield was 5.16 g (41.2%),
1
m.p. 140 °C (cf. Ref. 4: m.p. 140 °C). H NMR, δ: 2.4 (s, 3 H,
References
Me); 6.35 (s, 2 H, CH2); 7.38 (d, 2 H, C6H4, J = 8.5 Hz); 7.74
(d, 2 H, C6H4, J = 7.9 Hz); 8.9 (s, 1 H, C(5)H). IR, ν/cm–1
:
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3138, 1664, 1558, 1515, 1471, 1440, 1425, 1380, 1309, 1284, 1234,
1199, 1134, 1056, 1033, 966. Found (%): C, 40.3; H, 3.5;
N, 18.9. C10H10N4O5S. Calculated (%): C, 40.3; H, 3.4; N, 18.8.
1ꢀ(Azidomethyl)ꢀ3ꢀnitroꢀ1Hꢀ1,2,4ꢀtriazole (5). A mixture of
compound 4 (3.0 g, 0.01 mol) and sodium azide (1.6 g, 0.024 mol)

Derivatives of 3ꢀnitroꢀ1,2,4ꢀtriazole
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Received May 5, 2009;
in revised form October 16, 2009