Synthesis of 1,6-dihydro-1,6-dihydroxybenzo[1,2-d:3,4-d′]bistriazole, 4- and 5-nitro-1,6-dihydro-1,6-dihydroxybenzo[1,2-d:3,4-d′]bistriazole and 4,7-dihydro-1,4,7-trihydroxy-1H-benzo-[1,2-d:3,4-d′:5,6-d″] tris[1,2,3]triazole

Article abstract of DOI:10.1007/s11172-012-0244-x

1,6-Dihydro-1,6-dihydroxybenzo[1,2-d:3,4-d′]bistriazole and 4- and 5-nitro-1,6-dihydro-1,6-dihydroxybenzo[1,2-d:3,4-d′]bistriazole were synthesized starting from 2,4-dinitrosore-sorcinol, whereas 4,7-dihydro-1,4,7- trihydroxy-1H-benzo[1,2-d:3,4-d′:5,6-d″]tris[1,2,3]-triazole was synthesized starting from phloroglucinol. The reaction of trinitrosophloroglucinol with hydrazine hydrate in acetic acid led to 2,4,6-tridiazocyclohexane-1,3,5-trione.

Full text of DOI:10.1007/s11172-012-0244-x

Russian Chemical Bulletin, International Edition, Vol. 61, No. 9, pp. 1776—1782, September, 2012
1776
Synthesis of 1,6ꢀdihydroꢀ1,6ꢀdihydroxybenzo[1,2ꢀd:3,4ꢀd´]bistriazole,
4ꢀ and 5ꢀnitroꢀ1,6ꢀdihydroꢀ1,6ꢀdihydroxybenzo[1,2ꢀd:3,4ꢀd´]bistriazole
and 4,7ꢀdihydroꢀ1,4,7ꢀtrihydroxyꢀ1Hꢀbenzoꢀ
[1,2ꢀd:3,4ꢀd´:5,6ꢀd]tris[1,2,3]triazole
V. A. Samsonov, Yu. V. Gatilov, and L. B. Volodarskii†
N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of Sciences,
9 prosp. Akad. Lavrent´eva, 630090 Novosibirsk, Russian Federation.
Fax: +7 (383) 330 9752. Eꢀmail: samson@nioch.nsc.ru
1,6ꢀDihydroꢀ1,6ꢀdihydroxybenzo[1,2ꢀd:3,4ꢀd´]bistriazole and 4ꢀ and 5ꢀnitroꢀ1,6ꢀdihydroꢀ
1,6ꢀdihydroxybenzo[1,2ꢀd:3,4ꢀd´]bistriazole were synthesized starting from 2,4ꢀdinitrosoreꢀ
sorcinol, whereas 4,7ꢀdihydroꢀ1,4,7ꢀtrihydroxyꢀ1Hꢀbenzo[1,2ꢀd:3,4ꢀd´:5,6ꢀd]tris[1,2,3]ꢀ
triazole was synthesized starting from phloroglucinol. The reaction of trinitrosophloroglucinol
with hydrazine hydrate in acetic acid led to 2,4,6ꢀtridiazocyclohexaneꢀ1,3,5ꢀtrione.
Key words: nitrosophenols, 1ꢀhydroxybenzotriazoles, 2Hꢀbenzotriazole Nꢀoxides, dihydroꢀ
benzo[1,2ꢀd:3,4ꢀd´]bistriazoles, benzotristriazoles, diazoketones.
Scheme 1
An important property of 1ꢀhydroxybenzotriazole is its
ability to liberate gaseous products upon heating, which
allow one to use it as a blowing agent in the production of
gasꢀfilled materials.1,2 The range of foaming agents is
limited, and a search for new compounds which satisꢀ
fy practical requirements remains still an actual probꢀ
lem. Introduction into the molecule of 1ꢀhydroxybenzoꢀ
triazole of groups capable of easy decomposition on
heating with the formation of gaseous products could
have broaden the scope of such compounds. Additional
one or two 1ꢀhydroxytriazole rings annulated to 1ꢀhydrꢀ
oxybenzotriazole could have served as such groups. In orꢀ
der to broaden the range of the gasꢀgenerating compounds,
we carried out synthesis of such 1ꢀhydroxybenzotriazoles.
The synthesis of 1ꢀhydroxybenzotriazole annulated to
another 1ꢀhydroxytriazole ring was effected according to
Scheme 1. The nitrosation of resorcinol 1 leads to 2,4ꢀdiꢀ
nitrosoresorcinol 2 (see Ref. 3). (Taking into account that
oꢀ and pꢀnitrosohydroxyarenes exist in the tautomeric
equilibrium with quinone oximes,4 to make the presentaꢀ
tion of the material easier, the nitrosation products of
hydroxyarenes further will be called as the corresponding
nitroso compounds.)
When compound 2 was treated with 2,4ꢀdinitropheꢀ
nylhydazine (2,4ꢀDNPH), 2,6ꢀdi[(2,4ꢀdinitrophenyl)ꢀ
hydrazono]cyclohexꢀ4ꢀeneꢀ1,3ꢀdione 1,3ꢀdioxime 3 was
formed (see Ref. 5). The oxidation of compound 3 with
MnO2 in acetone gave rise to 2,7ꢀdihydroꢀ2,7ꢀdi(2,4ꢀ
dinitrophenyl)benzo[1,2ꢀd:3,4ꢀd´]bistriazole 1,6ꢀdioxꢀ
Ar = 2,4ꢀ(NO2)2C6H3
Reagents, conditions, and yields: i. NaNO2, H2SO4, 0—3 C, 92%;
ii. 2,4ꢀDNPH, MeOH, HCI (gas), 20 C, 94%; iii. MnO2, acetone,
50 C, 61%; iv. MeONa, MeOH, 40 C, 61.4%; v. K2CO3, MeI,
MeCN, 54%.
†
Deceased.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1760—1766, September, 2012.
1066ꢀ5285/12/6109ꢀ1776 © 2012 Springer Science+Business Media, Inc.

Synthesis of hydroxybenzotriazoles
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 9, September, 2012
1777
1
ide (4). The structure of compound 4 was confirmed by
the 1H and 13C NMR data, as well as by mass spectromeꢀ
try and elemental analysis.
The H NMR spectrum of compound 7 exhibits sigꢀ
nals for six aromatic protons as multiplets at  8.38—8.40,
8.85—8.98, and 9.02—9.09 and a broad singlet at  9.00.
In the 13C NMR spectrum four signals for the carbon
atoms bonded to the hydrogen atoms and 11 signals for
the quaternary carbon atoms are found. Apparently, other
signals for the carbon atoms overlapped. In the mass specꢀ
trum of compound 7, a peak of the molecular ion with the
mass 589 is observed. The C18H7N11O12 molecular forꢀ
mula was obtained from the elemental analysis data.
A combination of these data allowed us to suggest that the
obtained compound 7 is a mononitro derivative of benzoꢀ
bistriazole.
To clarify which position (4 or 5) the nitro group is
situated at, we used recrystallization from dilute nitric
acid to grow crystals and performed Xꢀray diffraction studꢀ
ies of molecule 7. From the Xꢀray diffraction data, it folꢀ
lows that the product 7 is a mixture of 2,7ꢀdihydroꢀ2,7ꢀ
bis(2,4ꢀdinitrophenyl)ꢀ4ꢀnitrobenzo[1,2ꢀd:3,4ꢀd´]ꢀ
bistriazole 1,6ꢀdioxide (7a) and 2,7ꢀdihydroꢀ2,7ꢀbis(2,4ꢀdiꢀ
nitrophenyl)ꢀ5ꢀnitrobenzo[1,2ꢀd:3,4ꢀd´]bistriazole 1,6ꢀdiꢀ
oxide (7b) in the ratio of 7 : 3.
The structure of molecules 7a and 7b in the cocrystal is
shown in Fig. 1. The benzobistriazole fragment is planar,
with the mean square deviation of atoms being 0.048 Å.
The dinitrophenyl groups deviate from this plane by the
same angle of 65.2(1). The nitro group of the benzobisꢀ
triazole fragment of the molecule is disordered over
two positions, with the ratio of occupations being
0.708(7) : 0.292(7), which indicates cocrystallization of
two isomers, viz., 4ꢀnitroꢀ and 5ꢀnitrobenzobistriazoles
(7a and 7b, respectively). The nitro group at position 4 is
coplanar to the framework (the angle of 1.1(5)), whereas
the nitro group at position 5 deviates from the plane by the
angle of 21.1(8). Note that we did not find data on analoꢀ
gous benzobistriazole Nꢀoxides in the Cambridge Strucꢀ
tural Database.12 There are data on the structure of 4,6ꢀdiꢀ
nitroꢀ2ꢀ(2,4,6ꢀtrinitrophenyl)ꢀ2Hꢀbenzotriazole 1ꢀoxꢀ
ide,13 methyl 3ꢀ[3ꢀtertꢀbutylꢀ5ꢀ(6ꢀchloroꢀ1ꢀhydroxyꢀ
benzotriazolꢀ2ꢀyl)ꢀ4ꢀhydroxyphenyl]propionate,14 and
2ꢀ(3ꢀcarboxamidofuroxanꢀ4ꢀyl)ꢀ4ꢀnitroꢀ5ꢀcarboxamidoꢀ
2Hꢀ[1,2,3]triazole 1ꢀoxide.15 The bond distances of the
Since the molecule is unsymmetric, the signals for the
protons of the 4ꢀdinitrophenyl groups in the 1H NMR
spectrum of compound 4 are observed as multiplets at
 7.80—7.95, 8.30—8.41, and 9.80—9.95, the signals for
the protons at positions 4 and 5 as doublets at  9.02 and
9.03. The 13C NMR spectrum exhibits five signals for the
carbon atoms bonded to a hydrogen atom, and 10 signals
for the quaternary carbon atoms. Apparently, three signals
for the carbon atoms overlapped with other signals. As it
has been shown earlier, 2,4ꢀdinitrophenyl group in benzoꢀ
triazoles could be easily eliminated upon the action of
nucleophilic agents.6—9 The action on benzobistriazole 4
of sodium methoxide in methanol led to the elimination
of dinitrophenyl groups with the formation of 1,6ꢀdiꢀ
hydroꢀ1,6ꢀdihydroxybenzo[1,2ꢀd:3,4ꢀd´]bistriazole (5)
(see Scheme 1). It should be noted that in the mass specꢀ
trum of compound 5, the peak of molecular ion with the
mass 292 is absent and the peak with the mass 264 —
[M – 28]+ is present. Apparently, molecules of compound
5 in the source of ions of mass spectrometer decompose
with elimination of nitrogen.
It is known10 that 1ꢀhydroxybenzotriazole A exists in
the tautomeric equilibrium with its Nꢀoxide form B, with
the form B being predominant in polar solvents, whereas
the form A is predominant in nonpolar. Methylation of
1ꢀhydroxybenzotriazole leads to a mixture of Nꢀ and
Oꢀmethylated compounds.11
Upon alkylation of compound 5 with methyl iodide,
only Oꢀmethylated compound, i.e., dimethoxy derivative
6, was isolated (see Scheme 1).
Treatment of compound 3 with nitric acid led to comꢀ
pound 7 (Scheme 2).
Scheme 2
Reagents, conditions, and yields: i. HNO3 (d = 1.42), reflux, 43%; ii. MeONa, MeOH, 40 C, 50.4%.

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Samsonov et al.
O(2)
N(4)
C(4)
O(10)
of dinitrophenyl groups and formation of a mixture of
1,6ꢀdihydroꢀ1,6ꢀdihydroxyꢀ4ꢀnitrobenzo[1,2ꢀd:3,4ꢀd´]ꢀ
bistriazole (8a) and 1,6ꢀdihydroꢀ1,6ꢀdihydroxyꢀ5ꢀnitroꢀ
benzo[1,2ꢀd:3,4ꢀd´]bistriazole (8b), respectively (see
O(3)
O(2A)
O(11)
N(1)
N(10)
O(9)
C(11)
N(3)
N(4A)
1
C(12)
Scheme 2). In the H NMR spectrum of the mixture of
O(12)
C(3A) N(2)
C(8B)
C(9)
O(3A)
C(5)
compounds 8a and 8b, the following signals for the hydroꢀ
gen atoms are observed: for compound 8a at  8.36, for
compound 8b at  8.34, as well as a broad signal at  10.4
for the hydrogen atoms of two OH groups. Note that both
isomeric compounds have identical 13C NMR spectra.
The synthesis of 1ꢀhydroxybenzotriazole annulated
with two 1ꢀhydroxytriazole rings was carried out accordꢀ
ing to Scheme 3. The nitrosation of phloroglucinol 9 easiꢀ
ly leads to the formation of trinitrosophloroglucinol 10.
The synthesis of this compound was described in the
works.16,17 The compound was isolated as a potassium
salt. The free trinitrosophloroglucinol was obtained by deꢀ
composition of the lead salt with alcoholic sulfuric acid.
Both the potassium salt and the free trinitrosophloroꢀ
glucinol are unstable. The product 10 rapidly decomposes
on standing in aqueous solutions and especially during
evaporation of these solutions. We found that the free triꢀ
nitrosophloroglucinol 10 was easily obtained upon nitroꢀ
sation of phloroglucinol isopropylnitrite in ethanol in
the presence of catalytic amounts of acetic acid. The reacꢀ
tion of compound 10 with 2,4ꢀDNPH led to 2,4,6ꢀtriꢀ
[(2,4ꢀdinitrophenyl)hydrazono)]cyclohexaneꢀ1,3,5ꢀtrione
1,3,5ꢀtrioxime 11, whose oxidation with MnO2 in acetone
C(13)
C(14)
C(5A)
N(1)
O(4)
O(1)
C(8A)
N(7)
N(6)
O(1W)
N(5)
O(6)
N(8)
O(5)
C(15)
C(20)
C(19)
O(2W)
O(3W)
C(16)
C(18)
O(8)
C(17)
N(9)
O(7)
Fig. 1. Molecular structures of 4ꢀ and 5ꢀnitroꢀ2,7ꢀdihydroꢀ2,7ꢀ
di(2,4ꢀdinitrophenyl)benzo[1,2ꢀd:3,4ꢀd´]bistriazole 1,6ꢀdioxides
(7a,b) in the cocrystal (the solvent molecules of water are shown).
The distances are as follows: O(1)...O(2W) 2.86(2), O(2W)...O(3W)
2.77(4), O(3W)...O(1W) 2.44(5) Å.
triazole oxide fragment of the cocrystal under studies are
close to the data given in the literature.
The action on a mixture of benzotriazoles 7a and 7b of
sodium methoxide in methanol leads to the elimination
Scheme 3
R = H (13), OMe (14)
Reagents, conditions, and yields: i. PriONO, MeOH, AcOH, 0—5 C, 95%; ii. 2,4ꢀDNPH, MeOH, HCl (gas), 20 C, 93%; iii. MnO2,
acetone, 40 C, 35%; iv. MeONa, MeOH, 40 C, 54.5%; v. NH2NH2•H2O, AcOH, reflux, 20.5%.

Synthesis of hydroxybenzotriazoles
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 9, September, 2012
1779
or with nitric acid gave benzotristriazole 1,4,7ꢀtrioxide 12.
The product is a light yellow crystalline compound with
melting point above 360 C, virtually insoluble in water
and ethanol. Compound 12 is very poorly soluble in aceꢀ
tone and was recrystallized from 70% aqueous nitric acid.
Because of poor the solubility of the compound in organic
solvents, the NMR spectra were recorded in concentrated
C(7)
N(1)
N(2)
O(1)
C(6)
N(3)
N(9)
C(1)
C(2)
1
sulfuric acid. The H NMR spectra exhibit three broad
N(4)
N(8)
signals for the hydrogen atoms of the dinitrophenyl groups
in the region  7.75—7.95, 8.40—8.60, and 8.75—8.94.
The 13C NMR spectra exhibit eight signals for the carbon
atoms, the three of which belong to the carbon atoms
bonded to the hydrogen atoms in the dinitrophenyl groups.
Other three signal are attributable to the carbon atoms,
which are not bonded to the hydrogen atoms in the diꢀ
nitrophenyl groups, and other two signals belong to the
carbon atoms of the triazole rings.
O(2)
C(8)
C(3)
C(5)
N(7)
O(3)
C(4)
N(6)
N(5)
C(9)
Fig. 2. Molecular structure of 4,7ꢀdihydroꢀ1,4,7ꢀtrimethoxyꢀ1Hꢀ
benzo[1,2ꢀd:3,4ꢀd´:5,6ꢀd]tris[1,2,3]triazole (14).
Elimination of 2,4ꢀdinitrophenyl groups in compound
12 upon the action of MeONa in methanol led to the
formation of trihydroxybenzotristriazole 13. This comꢀ
pound was obtained as colorless crystals and is insoluble
in most organic solvents, including DMSO and DMF,
moderately soluble in water, but well soluble in aqueous
solutions of acids and alkali. Compound 13 was recrystalꢀ
lized from water. The 13C NMR spectrum recorded in
H2SO4 exhibits two signals for the carbon atom at  129.00
and 123.5. A peak of molecular ion with the mass of 249 is
present in the mass spectrum. The C6H3N9O3•3H2O moꢀ
lecular formula was calculated for the compound from the
elemental analysis data. These data allowed us to assign to
the compound obtained the structure of 4,7ꢀdihydroꢀ1,4,7ꢀ
trihydroxyꢀ1Hꢀbenzo[1,2ꢀd:3,4ꢀd´:5,6ꢀd]tris[1,2,3]triꢀ
azole (13).
oxy groups deviate from the plane of the framework, the
torsional angles CNOC are equal to –88.7(3), 88.2(3),
and 100.4(3), indicating that one methoxy group comes
out of the plane to the opposite side. According to
the gasꢀphase DFT/B3LYP/6ꢀ311G* calculations, such
a ꢀconformation is only 0.2 kcal mol–1 more stable
than the ꢀconformation, the rotational barrier for the
methoxy group is equal to 6.0 kcal mol–1. Molecules in the
crystal form stacks along the axis a due to the ꢀstacking
(the distances: between planes 3.32 Å, intercentroid
3.425(1), 3.717(1) Å (benzene—triazole) and 3.665(1) Å
(triazole—triazole)). The following interactions between
stacks C—H...O (C(8)—H...O(2), H...O 2.63 Å, C—H...O
154; C(9)—H...O(2), 2.61, 140; C(9)—H...O(3), 2.55,
164) combine the stacks in layers.
It is necessary to note that the reaction of trinitroꢀ
sophloroglucinol 10 with hydrazine hydrate in acetic acid
unexpectedly led to 2,4,6ꢀtridiazocyclohexaneꢀ1,3,5ꢀtriꢀ
one (15) instead of the expected 2,4,6ꢀtrihydrazonocycloꢀ
hexaneꢀ1,3,5ꢀtrione 1,3,5ꢀtrioxime. Compound 15 has
been obtained earlier by the reaction of 2ꢀazidoꢀ3ꢀethylꢀ
benzothiazolium fluoroborate with phloroglucinol.20 The
formation of compound 15 can be explained similarly to
the described synthesis of 3ꢀdiazoꢀ2,4ꢀchromanedione.21 It
is possible that the reaction of the nitroso group in triꢀ
nitrosophloroglucinol with hydrazine hydrate results
in the formation the intermediate triazene, eliminaꢀ
tion of ammonia from which gives rise to compound 15
(Scheme 4).
The alkylation of compound 13 with methyl iodide
easily led to the formation of 4,7ꢀdihydroꢀ1,4,7ꢀtriꢀ
methoxyꢀ1Hꢀbenzo[1,2ꢀd:3,4ꢀd´:5,6ꢀd]tris[1,2,3]triazole
(14). The structure of compound 14 was confirmed by the
Xꢀray diffraction data (Fig. 2).
The molecular framework of compound 14 is planar
within 0.021 Å (see Fig. 2). The carbocycle of the moleꢀ
cule demonstrates clear alternation of the bond distances:
the bonds common to two rings have the lengths of
1.385(3)ꢀ1.389(3) Å, other bonds lie within 1.430(3)—
1.432(3) Å. Such an alternation agrees with the quantum
chemical calculations, which gives 1.408 and 1.423 Å
(DFT/PBE/3z), 1.402 and 1.423 Å (DFT/B3LYP/6ꢀ
311G*), respectively. Similar alternation of bond distancꢀ
es was observed in the molecule of 2,5,8ꢀtriꢀnꢀpentylꢀ
benzotris(imidazole)18 (1.375(6) and 1.408(6) Å), howevꢀ
er, in the molecule of 2,5,8ꢀtris(4ꢀmethylphenyl)bisꢀ
[1,3]dithiolo[4,5ꢀe:4´,5´ꢀg][1,3]benzodithiole,19 the alterꢀ
nation was reverse (1.414(5) and 1.378(5) Å). The bond
distances in heterocycles also are close to the calculated
values and slightly differ from the data for the molecule of
1ꢀhydroxybenzotriazole.10 In the molecule 14, the methꢀ
In conclusion, we for the first time accomplished synꢀ
thesis of a number (5, 6, 8, 13, 14) of 1ꢀhydroxyꢀ and
1ꢀmethoxybenzotriazoles annulated to one and two 1ꢀhyꢀ
droxytriazole rings. Preliminary testing showed that these
compounds are promising gasꢀgenerating components in
the corresponding devices. Thus, heating of 1 g of comꢀ
pound 5 in an autoclave at 250 C during 10 min results in

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Samsonov et al.
Scheme 4
The gasꢀphase quantum chemical calculations were perꢀ
formed using the PRIRODA program (DFT/PBE/3z) and the
GAMESS program (DFT/B3LYP/6ꢀ311G*).
Crystallographic data for the cocrystal of compounds 7a and 7b.
Temperature 296 K, C18H7N11O12 + 0.621(H2O), M = 580.51,
triclinic crystal system, space group P1–, a = 10.836(4) Å,
b = 11.410(4) Å, c = 11.772(3) Å,  = 77.72(3),  = 63.14(2),
 = 80.83(3), V = 1265.4(7) Å3, Z = 2, dcalc = 1.515 g cm–3
,
 = 0.132 mm–1, scanning range 2 < 50, number of measured
reflections 4706 (Rint = 0.0506), number of reflections with
I  2(I) 2280, number of refined parameters 396, R1(I  2(I)) =
= 0.0856, wR2 = 0.2792, S = 1.010 (on all the 4432 independent
reflections). Allowance for absorption was made using experiꢀ
mental curves of the azimuth scanning (Tmin/Tmax = 0.6381/
0.8846). The crystalline structure showed the presence of the
water solvent molecules placed in three positions. It should be
noted that these positions are occurred partially (0.156(9),
0.337(10), 0.128(9)), that is apparently due to the loss of the
water molecules on storage of the crystals. This is facilitated by
the molecular packing, which creates channels along the axis c
with the overall volume of 231.7 Å3.
i. NH2NH2•H2O; ii. –NH3.
the liberation of 700 mL of gases, i.e., the compound has
high gas number. For comparison, it can be indicated that
1 g of oxygen occupies the volume of 700 mL.
Experimental
Crystallographic data for compound 14. Temperature 200 K,
C9H9N9O3, M = 291.25, monoclinic crystal system, space
group P21/c, a = 4.0975(6), b = 18.109(3), c = 16.891(2) Å,
IR spectra were recorded on a Bruker Vector spectrometer
in KBr pellets (concentration of 0.25%). UV spectra of solutions
of compounds in ethanol were recorded on a Specord Mꢀ40
spectrophotometer. 1H and 13C NMR spectra were recorded on
a Bruker AM 400 spectrometer (400.13 (1H) and 100.61 MHz
 = 95.281(7), V = 1248.0(3) Å3, Z = 4, dcalc = 1.550 g cm–3
,
 = 0.123 mm–1, scanning range 2 < 50, amount of measured
reflections 5200, from them 2190 were independent (Rint
=
(
13C)) in DMSOꢀd6 and H2SO4 for 10% solutions at 25 C. Sulꢀ
= 0.0556), wR2 = 0.1182, S = 0.963, 191 parameter, R = 0.0449
furic acid of reagent grade (GOST 4204ꢀ77) was used for the
for 1409 F > 4 . Allowance for absorption was made by empiriꢀ
F
spectra recording, CH2Cl2 was used as an internal standard (H 5.33
cal method using the SADABS program (transmission 0.73—0.93).
Note that the Cambridge Structural Database12 has no informaꢀ
tion on benzobistriazoles and benzotristriazoles.
and  54.0). Chemical shifts were measured relative to the reꢀ
C
sidual signals of the solvent: DMSOꢀd6 ( 2.50 and  39.50).
H
C
Splitting of signals in the 13C NMR spectra was determined in
the Jꢀmodulation regime (JMOD). Mass spectra were recorded
on a Finnigan MATꢀ8200 instrument (70 eV, direct injection of
compounds, temperature the source of ions 180 C). Peaks of
molecular ions and peaks with intensities higher than 10% are
reported. Reaction progress and individuality of compounds were
monitored by TLC on Sorbfil UVꢀ254 plates. Chromatographic
plates were visualized with UV light and iodine vapors. Comꢀ
pounds 2 and 3 were synthesized according to the known proceꢀ
dures.3,5 Manganese dioxide (TU 6ꢀ09ꢀ01ꢀ718ꢀ87) purchased
from Leningrad plant Krasnyi khimik was used in the synthesis.
Melting points were determined on a Kofler microheating stage.
Elemental analysis of compounds was performed in the Laboraꢀ
tory of microanalysis of the Institute of Organic Chemistry,
Siberian Branch of the Russian Academy of Sciences.
Xꢀray diffraction studies were performed on a Bruker P4 difꢀ
fractometer (for compounds 7a and 7b, graphite monochromaꢀ
tor, (MoꢀK) = 0.71073 Å, /2ꢀscan technique) and Bruker
KAPPA APEX II diffractometer (for compound 14, MoꢀK
irradiation, graphite monochromator, ,ꢀscan technique). The
structures were solved by direct method using the SHELXSꢀ97
program. Refinement of the structural parameters were perꢀ
formed by the least squares method on all the reflections in fullꢀ
matrix anisotropic (for all the nonhydrogen atoms) approximaꢀ
tion using the SHELXLꢀ97 program. Positions of hydrogen atoms
were refined using the riding model. Full tables of the atomic
coordinates for compounds 7a, 7b, and 14 were deposited with
the Cambridge Structural Database (CCDC 822784 and CCDC
822785, respectively).
2,6ꢀDi[(2,4ꢀdinitrophenyl)hydrazono]cyclohexꢀ4ꢀeneꢀ1,3ꢀdiꢀ
one 1,3ꢀdioxime (3). 2,4ꢀDinitrophenylhydrazone (3.96 g, 0.02 mol)
was added to a solution of dinitrosoresorcinol 2 (1.68 g, 0.01 mol)
in methanol (300 mL) and a flow of dry HCl was passed through
the mixture with stirring at room temperature, then the mixture was
kept at room temperature for 8 h. A precipitate was filtered off,
washed with methanol, dried. The yield was 5.0 g (94%), comꢀ
pound 3 turns color to black at 270 C and does not melt to 360 C
(cf. Ref. 5: m.p. 266 C). Found (%): C, 40.80; H, 2.18; N, 26.42.
C18H12N10O10. Calculated (%): C, 40.92; H, 2.29; N, 26.51.
2,7ꢀDihydroꢀ2,7ꢀbis(2,4ꢀdinitrophenyl)benzo[1,2ꢀd:3,4ꢀd´]ꢀ
bistriazole 1,6ꢀdioxide (4). Manganese dioxide (20 g) was added
to a solution of compound 3 (3.80 g, 0.00715 mol) in acetone (1 L)
and the mixture was stirred for 24 h at 40—50 C. A precipitate
was filtered off, placed into the Soxhlet extractor and extracted
with hot acetone. Acetone was evaporated, the residue was susꢀ
pended in hexane, and a precipitate was filtered off. The yield of
bistriazole 4 was 2.38 g (61%), m.p. 167—169 C (decomp.,
ethanol). Found (%): C, 41.32; H, 1.73; N, 26.24. C18H8N10O10
.
Calculated (%): C, 41.22; H, 1.53; N, 26.72. UV, max/nm (lg ):
272 (3.30); 330 (3.15). 1H NMR (DMSOꢀd6), : 7.80—7.95
(m, 2 H, CH); 8.30—8.40 (m, 2 H, CH); 9.80—9.95 (m, 2 H, CH);
9.02 (d, 1 H, J = 2.0 Hz); 9.03 (d, 1 H, J = 2.0 Hz). 13C NMR
(DMSOꢀd6), : 116.87, 119.84, 121.34, 129.70, 131.45 (all CH);
114.87, 123.31, 129.16, 129.37, 131.37, 143.06, 143.50, 143.66,
148.69, 148.76 (all C). MS, m/z (Irel (%)): 524 [M]+ (40);
299 (10); 195 (20).
1,6ꢀDihydroꢀ1,6ꢀdihydroxybenzo[1,2ꢀd:3,4ꢀd´]bistriazole
(5). The compound MeONa (13.5 g, 0.25 mmol) was added to

Synthesis of hydroxybenzotriazoles
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 9, September, 2012
1781
a suspension of benzobistriazole 4 (20 g, 0.038 mol) in methanol
(500 mL), and the mixture was stirred for 6 h at 35—40 C,
followed by evaporation to dryness. Chloroform (300 mL) was
added to the residue, a precipitate formed was filtered off, thorꢀ
oughly washed with chloroform, and dried. A precipitate was
dissolved in water (200 mL), acidified with 10% aqueous HCI to
pH 5. A precipitate formed was filtered off, washed with water,
and dried to obtain compound 5 (4.50 g, 61.4%), m.p. 250 C
(decomp., ethanol). Found (%): C, 37.20; H, 2.08; N, 42.92.
C6H4N6O2. Calculated (%): C, 37.50; H, 2.10; N, 43.74. UV,
m.p. 220 C (decomp. from ethanol). Found (%): C, 30.20;
H, 2.08; N, 41.66. C6H3N7O4. Calculated (%): C, 30.39; H, 1.28;
1
N, 41.35. UV, max/nm (lg ): 270 (4.00); 340 (3.90). H NMR
(DMSOꢀd6), : 8.34 (8b: s, 1 H, CH); 8.36 (8a: s, 1 H, CH); 10.4
(br.s, 2 H, OH). 13C NMR (DMSOꢀd6), : 107.76 (CH); 120.70,
125.70, 130.69, 133.95, 137.72. MS, m/z (Irel (%)): 237 [M]+ (41).
2,4,6ꢀTrinitrosobenzeneꢀ1,3,5ꢀtriol (10). Acetic acid (0.5 mL)
was added to a solution of phloroglucinol dihydrate 9 (8.1 g,
0.05 mol) in methanol (80 mL). The mixture was cooled to 0 C,
followed by a dropwise addition of isopropyl nitrite (21.6 mL,
0.208 mol) with stirring and keeping the temperature in the mass
around 0—3 C. The addition time was ~1.5 h. The mixture was
stirred for 0.5 h at 0 C and another 0.5 h at room temperature.
The solvent was evaporated in vacuo of a waterꢀjet pump, keepꢀ
ing the temperature of the water bath below 35 C. The residue
was suspended in diethyl ether, a precipitate was filtered off,
washed with some diethyl ether, and dried to obtain comꢀ
pound 10•H2O (11.0 g, 95%), m.p. 126 C (decomp., ethanol).
Found (%): C, 31.20; H, 2.08; N, 18.32. C6H3N3O6·H2O. Calꢀ
culated (%): C, 31.17; H, 2.16; N, 18.18. UV, max/nm (lg ):
243 (4.13), 290 (4.29). 13C NMR (DMSOꢀd6), : 147.59, 172.48.
2,4,6ꢀTris[(2,4ꢀdinitrophenyl)hydrazono]cyclohexaneꢀ1,3,5ꢀ
trione 1,3,5ꢀtrioxime (11) was obtained according to the proꢀ
cedure similar to that for the synthesis of compound 3. The yield
of compound 11 was 93%, dark red crystalline compound,
m.p. > 360 C, insoluble in water, ethanol, moderately soluble in

max/nm (lg ): 230 (4.08). 1H NMR (DMSOꢀd6), : 7.61 (d, 1 H,
J = 10.0 Hz); 7.99 (d, 1 H, J = 10.0 Hz); 11.70 (br.s, 2 H,
OH). 13C NMR (DMSOꢀd6), : 107.89, 119.75 (all CH);
119.27, 127.80, 128.99, 141.58 (all C). MS, m/z (Irel (%)): 164
[M – 28]+ (3.6).
1,6ꢀDihydroꢀ1,6ꢀdimethoxybenzo[1,2ꢀd:3,4ꢀd´]bistriazole
(6). A. Finely powdered calcined potash (1.4 g, 0.01 mol) and
methyl iodide (1.4 g, 0.01 mol) were added to a solution of
compound 5 (0.3 g, 0.0016 mol) in anhydrous acetonitrile with
stirring. The mixture was stirred for 24 h at 25—30 C. A precipꢀ
itate formed was filtered off, the solvent was evaporated in vacuo
of a waterꢀjet pump, the residue was subjected to chromatoꢀ
graphy on SiO2, using chloroform as an eluent, to isolate comꢀ
pound 6 (0.25 g, 54%), m.p. 166—168 C (ethyl acetate). Found (%):
C, 43.46; H, 3.68; N, 38.27. C8H8N6O2. Calculated (%):
C, 43.63; H, 3.64; N, 38.18. UV, max/nm (lg ): 230 (4.60), 283
(3.05). 1H NMR (DMSOꢀd6), : 4.46 (s, 3 H, OCH3); 4.53 (s, 3 H,
OCH3); 7.85 (d, 1 H, J = 9.0 Hz); 8.19 (d, 1 H, J = 9.0 Hz).
13C NMR (DMSOꢀd6), : 68.35 (OCH3); 69.03 (OCH3); 107.97,
120.84 (all CH), 117.82, 126.98, 128.18, 141.53 (all C). MS, m/z
(Irel (%)): 220 [M]+ (17), 192 (70), 164 (17), 161 (10), 118(62),
103(69). HRMS: found m/z = 220.0707; C8H8N6O2; calculated,
M = 220.0703.
acetone. Found (%): C, 38.20; H, 2.08; N, 27.42. C24H15N15O15
.
Calculated (%): C, 38.25; H, 1.99; N, 27.89.
5,8ꢀDihydroꢀ2,5,8ꢀtris(2,4ꢀdinitrophenyl)ꢀ2Hꢀbenzo[1,2ꢀ
d:3,4ꢀd´:5,6ꢀd]tris[1,2,3]triazole 1,4,7ꢀtrioxide (12). A. Benzoꢀ
tristriazole 12 (35%) was obtained from compound 11 according
to the procedure similar to that for compound 4, m.p. > 360 C (70%
HNO3). Found (%): C, 38.20; H, 1.08; N, 27.82. C24H9N15O15
.
B. Dimethyl sulfate (2 g, 0.0158 mol) was added to a solution
of compound 5 (0.3 g, 0.0016 mol) in 10% aq. NaOH (10 mL),
the mixture was stirred at room temperature for 12 h, diluted
with water (10 mL), and extracted with ethyl acetate (3×15 mL).
A combined ethyl acetate extract was washed with saturated aq.
NaCl (2×20 mL) and dried with MgSO4. The solvent was evapoꢀ
rated in vacuo of a waterꢀjet pump, the residue was subjected to
chromatography on SiO2, using chloroform as an eluent to isoꢀ
late compound 6 (0.21 g, 61%).
4ꢀ and 5ꢀNitroꢀ2,7ꢀdihydroꢀ2,7ꢀbis(2,4ꢀdinitrophenyl)benzoꢀ
[1,2ꢀd:3,4ꢀd´]bistriazole 1,6ꢀdioxide (7a,b). Compound 3 (11.6 g,
0.025 mol) was added in portions to 70% aq. nitric acid (100 mL)
with stirring, the mixture was stirred for 2 h at room temperaꢀ
ture, then was heated to boiling, the reflux was continued for
30 min, and the mixture was allowed to stand for 16 h. A precipꢀ
itate formed was filtered off, washed with nitric acid, water, and
dried to obtain a mixture of bistriazoles 7a,b (6.12 g, 43%), m.p.
316 C (decomp., 70% HNO3). Found (%): C, 37.62; H, 1.38;
N, 27.16. C18H7N11O12. Calculated (%): C, 37.96; H, 1.23;
N, 27.07. 1H NMR (DMSOꢀd6), : 8.38—8.40 (m, 2 H, CH);
8.85—8.98 (m, 2 H, CH); 9.02—9.09 (m, 2 H, CH); 9.00 (br.s,
1 H, CH). 13C NMR (H2SO4), : 117.58, 122.31, 130.70, 132.83
(all CH); 120.37; 125.99; 128.21; 128.54; 129.86; 135.39; 139.02;
143.06; 143.14; 149.74; 149.94 (all C). MS, m/z (Irel (%)): 569
[M]+ (18); 195 (20).
Calculated (%): C, 38.55; H, 1.20; N, 28.11. 1H NMR (H2SO4),
: 7.75—7.95 (br.s, 3 H, CH); 8.40—8.60 (br.s, 3 H, CH);
8.75—8.94 (br.s, 3 H, CH). 13C NMR (H2SO4), : 122.15, 130.54,
132.45 (all CH); 118.84, 128.30, 130.33, 143.10, 149.53 (all C).
B. Compound 11 (20 g, 0.0268 mol) was added in portions to
70% aq. nitric acid (300 mL) and the mixture of was stirred at
room temperature for 3 h. Then, the reaction mass gradually was
heated to boiling and refluxed until a homogeneous solution was
formed. After cooling, a precipitate formed was filtered off,
washed with water and ethanol, and dried to obtain benzotristriꢀ
azole 12 (9 g, 45%).
4,7ꢀDihydroꢀ1,4,7ꢀtrihydroxyꢀ1Hꢀbenzo[1,2ꢀd:3,4ꢀd´:5,6ꢀ
d]tris[1,2,3]triazole (13) was obtained according to the proceꢀ
dure similar to that for the synthesis of compound 5. The yield
of compound 13 was 54.5%, m.p. 230 C (decomp.). Found (%):
C, 23.88; H, 2.56; N, 42.00. C6H3N9O3•3H2O. Calculated (%):
C, 23.76; H, 2.97; N, 41.58. 13C NMR (H2SO4), : 129.00,
123.52. MS, m/z (Irel (%)): 249 [M]+ (5.3).
4,7ꢀDihydroꢀ1,4,7ꢀtrimethoxyꢀ1Hꢀbenzo[1,2ꢀd:3,4ꢀd´:5,6ꢀ
d]tris[1,2,3]triazole (14). Finely powdered calcined K2CO3 (1.5 g)
and methyl iodide (6.84 g, 0.048 mol) were added to a suspenꢀ
sion of compound 13 (0.30 g, 0.00103 mmol) in DMF (15 mL)
and the mixture was stirred at room temperature for 12 h. The
solvent was evaporated in vacuo, the residue was diluted with
water (30 mL), a precipitate was filtered off, washed with water,
and dried. Purification was made by chromatography on SiO2,
using ethyl acetate—hexane (1 : 1) as an eluent to obtain comꢀ
pound 14 (0.22 g, 76%), m.p. 231—232 C (from ethyl acetate).
4ꢀ and 5ꢀNitroꢀ1,6ꢀdihydroꢀ1,6ꢀdihydroxybenzo[1,2ꢀd:3,4ꢀd´]ꢀ
bistriazole (8a,b) was obtained according to the procedure simiꢀ
lar to that for the synthesis of compound 5. The yield was 50.4%,

1782
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 9, September, 2012
Samsonov et al.
Found (%): C, 37.17; H, 3.03; N, 43.43. C9H9N9O3. Calculated
(%): C, 37.11; H, 3.09; N, 43.30. UV, max/nm (lg ): 230 (4.69).
1H NMR (DMSOꢀd6), : 4.57 (s, 9 H, 3 OCH3). 13C NMR
(DMSOꢀd6), : 69.30 (OCH3); 119.65, 128.41. MS, m/z
(Irel (%)): 291 [M]+ (32), 263 (25), 146 (72), 130 (31), 119 (32),
114 (100). MS: found m/z = 291.0820. C9H9N9O3; calculated,
M = 291.0823.
2,4,6ꢀTridiazocyclohexaneꢀ1,3,5ꢀtrione (15). Hydrazine hyꢀ
drate (2.5 mL, 0.05 mol) was added to a solution of trinitrosophloꢀ
roglucinol 10 (2.31 g, 0.01 mol) in acetic acid (100 mL). After
the exothermic the reaction reached completion, the reaction
mass was refluxed for 20 min. A precipitate was filtered off and
discarded. The filtrate was concentrated, the residue was subꢀ
jected to chromatography on SiO2, using ethyl acetate as an
eluent to obtain compound 15 (0.42 g, 20.5%), m.p. 228—229 C
(decomp., ethyl acetate; cf. Ref. 20: m.p. 220 C (benzene)).
Found (%): C, 35.60; N, 41.44. C6N6O3. Calculated (%): C,
35.29; N, 41.18. IR (KBr), /cm–1: 1620 (C=O); 2150
(C=N=N). UV, max/nm (lg ): 255 (4.58). 13C NMR (H2SO4),
: 85.64 (C=N=N), 169.98 (C=O). MS, m/z (Irel. (%)): 204
[M]+ (100).
for Inorganic Analysis], MGU Publ., Moscow, 1972, 198 pp.
(in Russian).
4. E. Yu. Belyaev, B. V. Gidaspov, Aromaticheskie nitrozosoꢀ
edineniya [Aromatic Nitroso Compounds], Khimiya, Leninꢀ
grad, 1989, 175 pp. (in Russian).
5. W. Borsche, H. Weber, J. Liebigs Ann. Chem., 1931, 489, 270.
6. E. Buncel, J. Dust, Can. J. Chem., 1988, 66, 1712.
7. J. Dust, E. Buncel, Can. J. Chem., 1991, 69, 978.
8. V. A. Samsonov, L. B. Volodarskii, V. L. Korolev, G. Kh.
Khisamutdinov, Khim. Geterotsikl. Soedin., 1993, 1364 [Chem.
Heterocycl. Compd. (Engl.Transl.), 1993, 29, 1169].
9. V. A. Samsonov, G. E. Sal´nikov, A. M. Genaev, Russ. Chem.
Bull. (Int. Ed.), 2009, 58, 2369 [Izv. Akad. Nauk, Ser. Khim.,
2009, 2294].
10. R. Bosch, G. Jung, W. Winter, Acta Crystallogr., Sect. C:
Cryst. Struct. Commun., 1983, 39, 1089.
11. O. L. Brady, C. V. Reynold, J. Chem. Soc., 1928, 193.
12. Cambridge Structural Database, Version 5.31 (Updates August
2010), University of Cambridge, Cambridge, UK.
13. R. A. Renfrow, M. J. Strauss, S. Cohen, E. Buncel, Aust. J.
Chem., 1983, 36, 1843.
Determination of amount of gases during decomposition of
1,6ꢀdihydroꢀ1,6ꢀdihydroxybenzo[1,2ꢀd:3,4ꢀd´]bistriazole (5).
Compound 5 (1.0 g) was placed in a 0.5ꢀL autoclave, which was
capped and heated at 250 C for 10 min using the Wood´s alloy.
After cooling to room temperature, a connecting pipe was used
to collects the liberated gas in a turned upside down and filled
with water graduated cylinder. It was found that 700 mL of the
gas was liberated.
14. H.ꢀL. Wen, Y.ꢀH. Chen, H.ꢀW. Hu, X.ꢀY. Zhou, C.ꢀB. Liu,
Acta Crystallogr., 2006, E62, o4702.
15. I. V. Ovchinnikov, M. A. Epishina, S. I. Molotov, Y. A.
Strelenko, K. A. Lyssenko, N. N. Makhova, Mendeleev Comꢀ
mun., 2003, 272.
16. R. Benedikt, Ber. Deutsch. Chem. Ges., 1878, 11, 1374.
17. K. Frandenberg, H. Fikentscher, W. Wenter, Justus Liebigs
Ann. Chem., 1925, 442, 309.
18. B. Kohne, K. Praefcke, T. Derz, T. Gondro, F. Frolow,
Angew. Chem., Int. Ed., 1986, 25, 650.
19. L. R. Sutton, W. A. Donaubauer, F. Hampel, A. Hirsch,
Chem. Commun., 2004, 1758.
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20. W. Ried, H. Mengler, Fortschr. Chem. Forsch., 1965, 5/1, 15.
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3. A. I. Busev, Sintezy novykh organicheskikh reagentov dlya
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Received June 27, 2011;
in revised form May 3, 2012