Structure and luminescence of thietane-containing 1,2,4-triazoles

Article abstract of DOI:10.1134/S1070363211060235

New thietane-containing 1,2,4-triazole derivatives were synthesized, and their structure was determined by ¹³C and ¹H NMR spectroscopy and mass spectrometry. The electronic absorption spectra of the new compounds in the ultraviolet and visible regions and their photoluminescence and luminescence excitation spectra were analyzed, and photoluminescence quantum yields were estimated. Pleiades Publishing, Ltd., 2011.

Full text of DOI:10.1134/S1070363211060235

ISSN 1070-3632, Russian Journal of General Chemistry, 2011, Vol. 81, No. 6, pp. 1203–1210. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © R.R. Kayumova, S.S. Ostakhov, A.V. Mamykin, R.R. Muslukhov, G.F. Iskhakova, S.P. Ivanov, S.A. Meshcheryakova, E.E. Klen,
F.A. Khaliullin, V.P. Kazakov, 2011, published in Zhurnal Obshchei Khimii, 2011, Vol. 81, No. 6, pp. 1010–1017.
Structure and Luminescence of Thietane-Containing
1,2,4-Triazoles
R. R. Kayumovaa, S. S. Ostakhova, A. V. Mamykina, R. R. Muslukhova, G. F. Iskhakovab,
S. P. Ivanova, S. A. Meshcheryakovab, E. E. Klenb, F. A. Khaliullinb, and V. P. Kazakov†a
a Institute of Organic Chemistry, Ufa Research Center, Russian Academy of Sciences,
pr. Oktyabrya 71, Ufa, 450054 Bashkortostan, Russia
e-mail: chemlum@anrb.ru
b Bashkir State Medical University, Ministry of Health Protection of the Russian Federation,
Ufa, Bashkortostan, Russia
Received May 25, 2010
Abstract—New thietane-containing 1,2,4-triazole derivatives were synthesized, and their structure was
1
determined by 13C and H NMR spectroscopy and mass spectrometry. The electronic absorption spectra of the
new compounds in the ultraviolet and visible regions and their photoluminescence and luminescence excitation
spectra were analyzed, and photoluminescence quantum yields were estimated.
DOI: 10.1134/S1070363211060235
1,2,4-Triazoles and their derivatives are fairly
extensively studied due to new possibilities for their
application both in medicine as biologically active
substances [1–3] and in optoelectronics [4–10]. 1,2,4-
Triazoles were also proposed as extractants for
transuranium elements [11]. Much attention is also
given to coordination compounds of 1,2,4-triazoles
with transition metals. As a rule, 1,2,4-triazoles are
coordinated to metal ions through the endocyclic
nitrogen atoms. Such ligands make it possible to
construct polymer matrices and cluster polynuclear
structures with silver, copper, cadmium, zinc, iron, and
iridium ions. 1,2,4-Triazole derivatives were also
introduced into polymer chain [12]. Studies in this
field are usually aimed at creating electroluminescent
devices (e.g., organic light-emitting diodes). Triazoles
are also used as catalysts for peroxyoxalate chemi-
luminescence [13], as well as in immunochemilumi-
nescence assay [14].
Introduction into triazole ring of various sub-
stituents, in particular oxothietane fragment, could
considerably extend the potential of the resulting
compounds as biologically active substances and
ligands for complex formation. As substituents we
tried thietane rings containing sulfur atom in different
oxidation states (i.e., as sulfide, sulfoxide, and sulfone
moieties) and benzylidenehydrazines. These fragments
were selected taking into account that thietane-
containing benzimidazoles and xanthines are known to
exhibit immunotropic, antimicrobial, and antiviral
activity [15, 16] and affect liver monooxygenase sys-
tem [17, 18] and that heterocyclic ylidenehydrazines
are structural fragments of such medical agents as
ftivazide, furagin, etc. [2].
In the present work we examined the structure of
compounds I–VII and their luminescence properties
which ensure their quantitative determination even at
very small concentration, e.g., in biological liquids
while studying their pharmacokinetics. The purity of
compounds I–VII was checked by HPLC, and their
Luminescence spectra of 1,2,4-triazoles and their
derivatives cover almost the entire visible region of the
spectrum. Variation of complexing metal ions, phase
state, substituents in the triazole ring, and polymer
matrix nature make it possible to change the emission
color over a wide range, from the blue region to red.
1
13
structure was confirmed by IR, H and C NMR, and
mass spectra. The NMR spectra of I–VII lacked
signals assignable to quaternary ammonium salts or
other impurities. The NMR spectra of I–III were
analyzed, and signals therein were assigned, by
comparing with the spectra of model 3,5-dibromo-1-
†
Deceased.
1203

1204
KAYUMOVA et al.
7
1
6
S
N N
N
S O
N
12
NO2
Br
NH N
C
13CH3
NO2
Br
Br
NH
5
N
C
N
N
CH3
I
II
O
S
N N
N
N NH
NH
N
O
C
NO2
NH N
Br
Br
N
N
IV
N
CH3
III
V
O
O
S
N
S
S
N
N
N N
N
NH NH2
NH NH2
Br
Br
Br
Br
N
N
VII
VI
VIII
13
1
(thietan-3-yl)-1,2,4-triazole (VI) and 3-bromo-5-hyd-
razino-1-(1,1-dioxo-λ6-thietan-3-yl)-1,2,4-triazole (VIII).
ring to the hydrazone fragment. The C and H NMR
spectra of compound III also contained signals
belonging to the other isomer, which was characterized
by different chemical shifts of carbon nuclei in the
hydrazine fragment. In keeping with the signal
intensities, the ratio of the cis and trans isomers was
estimated at 3:7.
The 13C NMR spectrum of VIII contains two
singlets at δC 127.84 and 140.81 ppm due to C3 and C5
in the triazole ring, a doublet at δC 54.53 ppm from the
N–CH carbon atom, and a triplet at δC 33.59 ppm from
two magnetically equivalent methylene carbon atoms
(CH2S) in the thietane ring. Compound VIII displayed
Figures 1 and 2 show the photoluminescence and
luminescence excitation spectra, respectively, of
compounds I–III, the corresponding spectra of IV–VII
are shown in Fig. 3, and the calculated luminescence
parameters are given in Table 1. Bromination of 1,2,4-
triazole IV at positions 3 and 5 (compound V) did not
change the spectral pattern in the short-wave region,
while a new long-wave absorption band appeared at λ
662 nm; the luminescence quantum yield of V was
higher than that found for compound IV by a factor of
9 in the blue region and by a factor of 1.6 in the red
region. Introduction of a thietanyl substituent into the
3,5-dibromo-1,2,4-triazole molecule changes the
fluorescence pattern in the short-wave region. Unlike
structured bands in the fluorescence spectra of IV and
V, the fluorescence spectrum of VI is represented by a
diffuse band with its maximum at λ 335 nm; the
emission spectra of IV–VI in the red region are
similar. Replacement of one bromine atom in molecule
VI by hydrazine fragment is accompanied by
variations in both short-wave (a new band appears at λ
412 nm) and long-wave regions (the band at λ 616 nm
disappears). Simultaneously, the short- and long-wave
fluorescence quantum yields increase (Φ = 0.014 and
0.006, respectively).
1
in the H NMR spectrum two doublets of doublets
from methylene protons in the cis (δ 3.31 ppm) and
trans positions (δ 4.08 ppm) with respect to the
triazolyl substituent in position 3 and a multiplet at δ
5.74 ppm from 3-H in the thietane ring. The coupling
constants for protons in the thietane ring are as
follows: 2J = –7.8, 3Jtrans = 8.3, 3Jcis = 7.9 Hz.
Molecules I–III possess an ylidenehydrazino group
on C5 in the triazole ring, as well as thietane (I), 1-oxo-
λ4-thietane (II), or 1,1-dioxo-λ6-thietane ring (III) on
the triazole N1 atom. The presence of two doublets at δ
1
8.31 and 8.10 ppm (3J = 8.2 Hz) in the H NMR
spectra of I–III corresponds to para-substitution of the
aromatic ring. Thietane fragments containing an sp2-
hybridized sulfur atom (sulfoxide S=O or sulfone
1
O=S=O) are characterized by reduced vicinal H–1H
coupling constants (3J = 4.5–4.8 Hz) and appreciable
downfield shift of methylene carbon signals (SCH2).
Signals from carbon nuclei in the triazole ring of
compounds I–III appear in a considerably weaker field
relative to those typical of model compound VI (up to
8 ppm). Presumably, the observed downfield shift
results from partial π-electron density transfer from the
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STRUCTURE AND LUMINESCENCE OF THIETANE-CONTAINING
1205
λex 520 nm
0.20
0.15
0.10
0.05
0.00
λex 270 nm
600
λ, nm
λ, nm
Fig. 2. Luminescence excitation spectra of compounds (1) I,
(2) II, and (3) III; c = 10–4 M, λem = 610 nm, slit width 10/10
nm, solvent DMSO, 20°C.
Fig. 1. Luminescence spectra of compounds (1) I, (2) II, and
(3) III; c = 10–4 M, slit width 15/15 nm, solvent DMSO, 20°C.
Among 1,2,4-triazole derivatives I–III, the highest
photoluminescence quantum yield was observed for
compound I (Φ = 1.5×10–5, Table 1). Oxidation of the
thietane ring to oxo-λ4-thietane sharply reduces the
fluorescence quantum yield down to 3×10–7, i.e., by a
factor of 40 as compared to 1,2,4-triazole. However,
contrary to the expectations, subsequent oxidation of
the sulfoxide group to sulfone (III) leads to increase of
the fluorescence quantum yield to 10–6. Presumably,
sharp reduction of the fluorescence quantum yield is
V
IV
0.20
0.15
20
15
0.10
0.05
0.00
10
5
0
λ, nm
VII
λ, nm
0.025
VI
0.020
0.015
0.010
0.005
0.000
λ, nm
λ, nm
Fig. 3. Luminescence excitation spectra of compounds IV–VII upon excitation at (1) λ 270 nm and (2) λ 520 nm (c = 10–3 M, slit
width 15/15 nm) and (3) luminescence excitation spectra (λem = 650 nm, slit width 10/10 nm), solvent DMSO, 20°C.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 6 2011

1206
KAYUMOVA et al.
II
I
λ, nm
λ, nm
III
V
λ, nm
λ, nm
Fig. 4. Luminescence excitation spectra of compounds I–III upon excitation at (1) λ 270 nm and (2) λ 520 nm (c = 10–4 M, slit width
15/15 nm) and (3) luminescence excitation spectra (λem = 650 nm, slit width 10/10 nm), solvent propan-2-ol, 20°C.
related to increased non-radiative loss of excitation
energy for vibrations of bonds in the substituent in
position 5 of the triazole ring.
VII; the only difference is appearance of a new band at
λ 356 nm in the spectrum of VII. Fluorescence
excitation spectra of 1,2,4-triazole derivatives I–III
revealed new luminescence bands in both short-wave
and long-wave regions. Analogous patterns were ob-
served for solutions of the same 1,2,4-triazole deriva-
There are no essential differences in the parameters
of fluorescence excitation spectra of compounds IV–
Table 1. Fluorescence parameters of compounds I–III (c = 10–4 M, λexcit = 270 nm, slit width 15/15 nm) and IV–VII (c = 10–3 M,
λexcit = 270, 520 nm, slit width 15/15 nm), DMSO, 20°Ca
Comp. no.
λex, nm
Sex
D (λexcit = 270 nm, l = 1 cm)
Sex/D
Φ × 105
270
270
270
270
520
270
520
270
520
270
520
12
0.6
1
990
11.1
930
13.6
280
0.4
2
5.3
2
6
0.1
0.5
2000
2800
18600
4500
2200
400
1.5
0.03
0.1
I
II
III
IV
0.5
50
0.004
0.05
0.003
0.13
0.001
0.21
0.0001
150
460
240
50
120
1360
590
V
VI
VII
5500
0.4
26200
4000
a
Hereinafter: Sex stands for the light sum, D is the optical density, and Φ is the fluorescence quantum yield.
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STRUCTURE AND LUMINESCENCE OF THIETANE-CONTAINING
1207
tives in propan-2-ol with a concentration of 10–4 M. A
I
A
A
few differences included the lack of some bands in the
luminescence and fluorescence excitation spectra, as
well as displacement of some luminescence maxima,
which may be attributed to the solvent effect (Fig. 4).
Two regions can be clearly distinguished in the
luminescence excitation spectra of all the examined
compounds. One of these is located in the visible and
ultraviolet areas (excitation with UV light), and the
other, in the red area (excitation with green light). The
red luminescence, regardless of its character and
nature, is unlikely to correspond to the p-nitrophenyl
fragment, for it is also intrinsic to derivatives having
no such fragment. Moreover, the red component is
much more intense for bromo-substituted triazoles.
Therefore, we believe that luminescence in the red
region corresponds to emission from triplet excited
triazole fragments. Increase in its intensity upon
replacement of hydrogen by bromine is the result of
heavy atom effect which favors triplet–singlet
transitions. We can conclude that fluorescence is
observed in the blue region and that phosphorescence
is observed in the red region. This conclusion
somewhat contradicts the luminescence spectra of
deoxygenated solutions (by purging with argon), which
were characterized by reduced emission intensity from
the expected triplet level. A reasonable explanation
implies that the lifetime of triazole molecule in the
triplet excited state is very short. Analogous pattern is
observed, e.g., for triplet excited molecules of some
ketones which are not deactivated by dissolved oxygen
as well [19].
λ, nm
II
A
A
λ, nm
III
A
A
λ, nm
Fig. 5. Electronic absorption spectra of compounds I–III in
the (1) ultraviolet and (2) visible regions (c = 10–4 M, l = 2 mm,
solvent DMSO, 20°C).
Solutions of I–III in DMSO change their color with
time. Immediately after dissolution, these solutions are
greenish; they turn green in a few minutes and then
become blue or violet. Change of the color is
accompanied by variation of the absorption spectra in
the visible region, whereas the spectral pattern in the
short-wave region remains almost unchanged. The
absorption maxima shift by 2–5 nm (Fig. 5). It was
surprising that variations of the color of solutions and
correspondingly of visible absorption spectra are not
reflected in the luminescence excitation spectra of
compounds I–III. The positions of maxima (λmax 270,
430–432, 512 nm) in the excitation spectra of bright
green and violet solutions of I–III do not change,
while their intensities change insignificantly. This
suggests that the color changes as a result of chemical
processes involving those chromophores which are not
responsible for fluorescence. In fact, differently colored
solutions of III are characterized by similar fluore-
scence spectra (λmax 337, 454–460, 550, 600 nm). The
color is also strongly affected by temperature and irradia-
tion. Photolysis of solutions of I–III under irradiation
with an SVD-120 mercury lamp leads to appearance of
yellow color whose intensity increases upon prolonged
irradiation, whereas the fluorescence intensity
simultaneously decreases. After irradiation over a
period of 2, the solutions become rich bright yellow,
and their fluorescence intensity becomes vanishingly
small (at a noise level). Presumably, irreversible
change of color upon photolysis is related to oxidation
processes. Taking into account that the sulfur atom in
the thietane ring of compound III occurs in the
maximal oxidation state, oxidation of other fragments,
e.g., hydrazino group, may be presumed.
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KAYUMOVA et al.
Table 2. Fluorescence parameters of tryptophan (c = 10–5 M)
at different slit widths of monochromator (SM-2203, DMSO,
20°C)
internal reference. The mass spectra (electron impact,
70 eV) were obtained on a Finnigan MAT 95 XP mass
spectrometer (ion source temperature 200°C; direct
sample admission into the ion source on heating from
50°C to 270°C at a rate of 22 deg/min). The precise m/
z values were determined in the range from 1 to 1000
a.m.u. at a resolution of 10000 at 10% of peak height
of all significant ions formed in the ion source) using
peak matching technique; perfluorokerosene was used
as reference. The electronic structure of compounds
was calculated at the RHF/3-21G* level of theory (PC
Gamess 7.0) with preliminary optimization of geo-
metric parameters.
D (λexcit = 260 nm,
Slit width, d, nm Sex
Sex/D
Φ
l = 1 cm)
15/15
10/10
10/5
1240
586
185
0.0234
0.0234
0.0234
52992 0.13
25043 0.13
7906 0.13
Unlike compound III, the sulfoxide group in the
thietane ring of II is capable of being oxidized to
sulfone. Photolysis of II is accompanied by
appreciable variations in the fluorescence excitation
spectra. After UV irradiation over a period of 30 min,
the absorption pattern typical of the initial solution
(λmax 310, 425, 465 nm) disappears, and a diffuse band
with its maximum at λ 400 nm arises. These variations
should inevitably be reflected in the fluorescence
spectra. In fact, the fluorescence spectrum of II before
irradiation displayed radiative transitions with their
maxima at λ 315 and 445 nm; after irradiation over a
period of 30 min, the corresponding maxima were
observed at λ 364 and 408 nm. In addition, the emis-
sion intensity changed considerably. Unlike sulfoxide
II, the fluorescence intensity of triazole VI did not
decrease after irradiation; by contrast, it increased. The
fluorescence quantum yields before and after irradia-
tion were 3×10–7 and 37×10–7, respectively. As noted
above, the fluorescence quantum yield for compound
III was thrice as high as that for II. We can conclude
that both variations in the excitation and emission
spectra and increase in the fluorescence quantum yield
after photolysis result from oxidation of the sulfoxide
sulfur atom to sulfone and that this process involves
the chromophore responsible for fluorescence.
The electronic absorption spectra were measured on
a Specord M-400 spectrophotometer (Carl Zeiss Jena).
The fluorescence emission and fluorescence excitation
spectra were recorded on an SM-2203 spectrofluori-
meter (Solar, Minsk, Belarus); spectral range 220–820
nm; maximal admissible error ∆pλ in setting
monochromator excitation and emission wavelength
±0.1 nm. Spectrophotometric measurements were
performed in the ultraviolet (λ 200–400 nm) and
visible regions (λ 450–700 nm) using 2-mm cells
against the corresponding solvent. The emission spec-
tra were recorded in the range from λ 250 to 700 nm;
luminescence excitation wavelengths 270 and 520 nm;
slit width 15/15 nm; 1-cm cell. The excitation spectra
were recorded in the range λ 250–600 nm, lumine-
scence wavelength 610 nm, slit width 10/10 nm. The
fluorescence quantum yields were determined relative
to D-tryptophan as reference according to the
procedure described in [20] (Table 2).
1H-1,2,4-Triazole (IV) and 3,5-dibromo-1H-1,2,4-
triazole (V) were synthesized according to the
procedures reported in [21] and [22], respectively. The
spectral parameters of compounds IV and V were
consistent with published data.
EXPERIMENTAL
3,5-Dibromo-1-(thietan-3-yl)-1H-1,2,4-triazole
HPLC analysis was performed on a Shimadzu LC-
20 instrument equipped with a spectrophotometric
diode matrix detector and a 250×4.6-mm column
packed with Luna C18 (grain size 5 μm; Phenomenex,
USA); isocratic elution, water–acetonitrile (50:50),
flow rate 1 ml/min; detection at λ 254 and 350 nm. The
1
(VI) was synthesized as described in [23]. H NMR
spectrum, δ, ppm (J, Hz): 3.77 d.d (2H, cis-CH2S, J =
8.8, 9.4), 3.98 d.d (2H, trans-CH2S, J = 8.8, 9.0), 6.10–
6.18 m (6-H), 13C NMR spectrum, δC, ppm: 33.59 t
(C7, C8), 54.53 d (C6), 140.81 (C5), 127.84 (C3).
1
13C and H NMR spectra were recorded on a Bruker
3-Bromo-1-(thietan-3-yl)-1H-1,2,4-triazol-5-yl-
hydrazine (VII). Hydrazine hydrate, 1.30 g of a
56.8% solution, was added to 1.02 g of 3,5-dibromo-1-
(thietan-3-yl)-1,2,4-triazole in 25 ml of butan-1-ol, and
the mixture was heated for 1 h under reflux and
evaporated to dryness under reduced pressure. The re-
AM-300 spectrometer at 75.5 and 300 MHz,
respectively. The 13C NMR spectra were measured
with broad-band decoupling from protons and with
J modulation (JMOD); DMSO-d6 and acetone-d6 were
used as solvents, and tetramethylsilane was used as
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 81 No. 6 2011

STRUCTURE AND LUMINESCENCE OF THIETANE-CONTAINING
1209
sidue was treated with 20 ml of distilled water
(2×10 ml), and the solvent was distilled off under
reduced pressure to remove excess hydrazine hydrate.
The precipitate was washed with water and dried.
Yield 0.75 g (75%), mp 175–176°C (from water). IR
spectrum, ν, cm–1: 1654 (C=N); 3028, 3142, 3208 (N–H).
1H NMR spectrum, δ, ppm (J, Hz): 3.24 d.d (2H, cis-
CH2S, J = 8.7, 9.0), 4.07 d.d (2H, trans-CH2S, J = 9.0,
9.2), 5.34–5.70 m (6-H), 7.6 br.s (NH, NH2). 13C NMR
spectrum, δC, ppm: 34.60 t (C7, C8), 55.65 d (C6),
131.69 s (C5), 139.41 s (C3).
1-[3-Bromo-1-(1,1-dioxo-λ6-thietan-3-yl)-1H-
1,2,4-triazol-5-yl]-2-[1-(4-nitrophenyl)ethylidene]hyd-
razine (III). Hydrochloric acid, 0.6 ml, and p-nitro-
acetophenone, 0.73 g (4.4 mmol), were added to a
solution of 1.13 g of 3-bromo-1-(1,1-dioxo-λ6-thietan-
3-yl)-1H-1,2,4-triazol-5-ylhydrazine in a mixture of
50 ml of ethanol and 10 ml of water. The mixture was
heated for 1 h under reflux and cooled, and the
precipitate was filtered off, washed with water, and
dried. Yield 1.27 g (75%), mp 263–265°C (from 1,4-
dioxane). IR spectrum, ν, cm–1: 1138, 1318 (SO2);
1142, 1588 (NO2); 1612 (C=N); 3280, 3304 (N–H). 1H
NMR spectrum, δ, ppm (J, Hz): 2.25 s (CH3, cis), 2.50
s (CH3, trans), 3.38 d.d (2H, cis-CH2SO2, J = 4.4, 4.8),
4.70 d.d (2H, trans-CH2SO2, J = 4.0, 4.4), 5.71–5.82 m
1-[3-Bromo-1-(thietan-3-yl)-1H-1,2,4-triazol-5-
yl]-2-[1-(4-nitrophenyl)ethylidene]hydrazine (I).
p-Nitro-acetophenone, 0.73 g, was added to a solution
of 1.00 g of 3-bromo-1-(thietan-3-yl)-1H-1,2,4-triazol-
5-ylhydrazine in 25 ml of ethanol. The mixture was
heated for 2 h under reflux and cooled, and the
precipitate was filtered off, washed with water, and
dried. Yield 1.42 g (89%), mp 182–184°C (from butan-
1-ol). IR spectrum, ν, cm–1: 1378, 1504 (NO2); 1612
(6-H), 8.25 d (2H, Harom, J = 7.8), 8.33 d (2H, Harom
,
J = 7.8), 8.30 d (2H, Harom, J = 7.9), 7.41 d (2H, Harom
,
J = 7.9). 13C NMR spectrum, δC, ppm: 13.70 q and
18.43 q (CH3), 39.54 d (C6), 70.71 t (C7, C8), 123.40 d
(Carom), 123.41 d (Carom), 126.86 d (Carom), 127.69 d
(Carom), 136.84 (C5), 140.18 (Carom), 143.93 (Carom),
147.30 (Carom), 148.05 (C3), 154.18 and 155.92 (C12).
Mass spectrum, m/z (Irel, %): 428 (60.6) [M]+, 105
(13.1), 324 (15.1), 163 (33.7), 117 (100), 76 (57.7),
382 (3.1).
1
(C=N); 3350 (N–H). H NMR spectrum, δ, ppm (J,
Hz): 2.55 s (3H, CH3), 3.89 d.d (2H, cis-CH2S, J = 8.8,
8.9), 4.03 d.d (2H, trans-CH2S, J = 8.9, 9.1), 6.11–6.32
m (6-H), 8.05 d and 8.31 d (2H each, Harom, J = 8.2),
13
9.62 br.s (NH). C NMR spectrum, δC, ppm: 13.66 q
(C13), 33.59 t (C7, C8), 54.50 d (C6), 124.53 d (Carom),
127.81 d (Carom), 137.83 (C5), 145.18 (Carom), 148.15
(Carom), 148.61 (C3), 153.32 (C12). Mass spectrum, m/z
(Irel, %): 396 (29) [M]+, 73 (100), 324 (93.8), 163 (12),
117 (39.3), 76 (21.2), 350 (10).
REFERENCES
1. Polya, Y.B., Comprehensive Heterocyclic Chemistry,
Katritzky, A.R. and Rees, C.W., Eds., Oxford:
Pergamon, 1984, vol. 5, p. 733.
1-[3-Bromo-1-(1-oxo-λ4-thietan-3-yl)-1H-1,2,4-tri-
azol-5-yl]-2-[1-(4-nitrophenyl)ethylidene]hydrazine
(II). p-Nitroacetophenone, 0.73 g, was added to a
solution of 1.06 g of 3-bromo-1-(1-oxo-λ4-thietan-3-
yl)-1H-1,2,4-triazol-5-ylhydrazine in 50 ml of ethanol.
The mixture was heated for 1.5 h under reflux and
cooled, and the precipitate was filtered off, washed
with water, and dried. Yield 1.50 g (91%), mp 246–
248°C (from 1,4-dioxane). IR spectrum, ν, cm–1: 1340,
1504 (NO2); 1598 (C=N); 3280–3600 (N–H). 1H NMR
spectrum, δ, ppm (J, Hz): 2.52 s (3H, CH3), 3.77 d.d
(2H, cis-CH2SO, J = 8.3, 8.7), 3.97 d.d (2H, trans-
CH2SO, J = 5.6, 8.7), 6.19–6.23 m (1H, 6-H), 8.10 d
and 8.32 d (2H each, Harom, J = 7.9), 9.34 br.s (NH).
13C NMR spectrum, δC, ppm: 13.69 q (C13), 56.73 t
(C7, C8), 56.80 d (C6), 123.60 d (Carom), 126.88 d
(Carom), 136.78 (C5), 143.94 (Carom), 146.88 (C3),
147.07 (Carom), 153.31 (C12). Mass spectrum, m/z (Irel,
%): 412 (68.2) [M]+, 89 (4.2), 324 (8.2), 163 (42.5),
117 (100), 76 (47.2), 366 (8.1), 349 (6.8).
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