Synthesis, structure, and spectral luminescent properties of novel 1,2,4-triazole derivatives containing benzthiazole group

Article abstract of DOI:10.1134/S1070363213110200

Novel derivatives of 1,2,4-triazol with benzthiazole fragment have been prepared, including Cu(II) and Be complexes. Their structure and spectral luminescent properties have been investigated. With ohydroxyphenylbenzthiazolyl- 1,2,4-triazole as an example

Full text of DOI:10.1134/S1070363213110200

ISSN 1070-3632, Russian Journal of General Chemistry, 2013, Vol. 83, No. 11, pp. 2075–2083. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © A.D. Beldovskaya, G.A. Dushenko, N.I. Vikrishchuk, L.D. Popov, Yu.V. Revinskii, I.E. Mikhailov, 2013, published in Zhurnal
Obshchei Khimii, 2013, Vol. 83, No. 11, pp. 1882–1891.
Synthesis, Structure, and Spectral Luminescent Properties
of Novel 1,2,4-Triazole Derivatives Containing Benzthiazole Group
A. D. Beldovskayaa, G. A. Dushenkob,c, N. I. Vikrishchukd,
L. D. Popovd, Yu. V. Revinskiib, and I. E. Mikhailovb,d
a Institute of Arid Zones, Southern Scientific Center, Russian Academy of Sciences, Rostov-on-Don, Russia
b Southern Scientific Center, Russian Academy of Sciences, Rostov-on-Don, Russia
c Research Institute of Physical and Organic Chemistry, Southern Federal University, Rostov-on-Don, Russia
d Southern Federal University, ul. Zorge 7, Rostov-on-Don, 344090 Russia
e-mail: natvi2004@mail.ru
Received May 14, 2013
Abstract―Novel derivatives of 1,2,4-triazol with benzthiazole fragment have been prepared, including Cu(II)
and Be complexes. Their structure and spectral luminescent properties have been investigated. With o-
hydroxyphenylbenzthiazolyl-1,2,4-triazole as an example, the density functional theory has been applied to find
the stable conformers with different structures of coordination nodes, stabilized by intramolecular hydrogen
bonds between hydroxyl group hydrogen and either triazole of benzthiazole nitrogen.
DOI: 10.1134/S1070363213110200
The recently emerged interest to 1,2,4-triazoles and
their derivatives is mainly due to their various bio-
logical activity [1–4] and excellent complexing ability
[5, 6]. The most remarkable complex formation
properties are revealed by o-hydroxyphenyltriazoles
containing =N(O)-phenol chelating node [7–11]; based
on them, a series of metal complexes with important
utilitarian properties has been prepared and charac-
terized [12–17]. Furthermore, being efficient and photo-
stable organic luminophors generating ultraviolet and
short-wavelength visible light, triphenyltriazoles have
been applied as elements of active laser media [18],
efficient electron transport materials in organic light-
emitting diodes (OLEDs) [19–21], and highly selective
fluorescent chemosensors for metal cations [22, 23].
o-Hydroxyphenyl-1,2,4-triazole
derivatives (IIIa–IIIc, IVa, and IVb) were prepared
using 4-oxo-1,3-benzoxazinium perchlorate I [24].
II
and
its
In particular, 5-(2'-hydroxyphenyl)-3-methyl-1-
benzthiazolyl-1,2,4-triazole II was obtained via
recyclization of the product of reaction between I and
benzthiazolylhydrazine; subsequent methylation of II
with methyl iodide in the presence of silver oxide gave
methyl ether (IIIa); treatment of II with acetic
anhydride in the presence of catalytic amounts of 70%
perchloric acid led to the acetate (IIIb); finally,
reaction of II with tosyl chloride and anhydrous
potassium carbonate in butanone resulted in the
tosylate (IIIc).
Structure of all the newly prepared compounds was
This work aimed to prepare novel derivatives of
1,2,4-triazole containing benzthiazole fragment,
including their metal complexes, and to elucidate their
structure as well as their spectral luminescent pro-
perties, important for OLED applications. Moreover,
as 5-(2'-hydroxyphenyl)-3-methyl-1-benzthiazolyl-1,2,4-
triazole II and its derivatives contain the pharma-
cophore benzthiazole and 1,2,4-triazole groups, the
prepared products will further extend the variety of
biologically active compounds of this class.
1
confirmed by elemental analysis, Н NMR, 13С NMR,
UV, IR, MS, quantum-chemical methods, and
electronic and fluorescent spectroscopy.
In the IR spectra of IIIa–IIIc, IVa, and IVb, the
stretching vibration bands of С=N and С=С were
observed at 1436–1620 cm–1. All those compounds
(including the ligand II) contained three different types
of C=N bonds: two in the triazole ring and one in the
benzthiazole fragment. Upon formation of the
2075

2076
BELDOVSKAYA et al.
CH3
CH3
N
M/2
N
OH
O
O
N
N
NH
NH2
N
S
M2+
N
N
NH
+
AcOH
S
S
O
CH3
N
N
ClO4_
I
II
IVa, IVb
CH3
N
OR
N
N
S
N
IIIa_IIIc
R = Me (IIIa), Ac (IIIb), Ts (IIIc); M = Be (IVa), Cu (IVb).
complexes IVa and IVb, the band of C5=N4 stretching
was shifted to lower frequencies by 24–30 cm–1 (to
1563–1575 cm–1) as compared with the corresponding
band in the triazoles II and IIIa–IIIc spectra (1593–
1599 cm–1), whereas IR properties of the two other
C=N bonds were less sensitive to complex formation.
Formation of IIIa–IIIc, IVa, and IVb from triazole II
was accompanied with vanishing of the ОН group
band at 3120 cm–1 (II) [11]. IR spectrum of the acyl
derivative IIIb revealed the intense bands at 1742 and
1764 cm–1 (C=O), evidently, due to pair of acyl
conformers; the spectrum of tosyl derivative IIIc
contained SO2 vibration bands at 1168 and 1368 cm–1.
7.5 Hz (IIIa), 162.57 ppm and 2JС,Н 7.5 Hz (IIIb), and
162.13 ppm and JСН 6.9 Hz (IIIc)] due to far spin-
2
spin interaction with protons of methyl group at C3; the
signal of С2'' in thiazole ring was singlet at 135.86 ppm
(IIIa), 156.90 ppm (IIIb), and 156.81 ppm (IIIc), as
4JС,Н far spin-spin interaction with aromatic protons
was not observed. The mentioned spectral features of
IIIa–IIIc coincided with the monoresonance 13С
spectra of II [11].
Mass spectra of IIIa–IIIc contained the molecular
ion peak and the peaks of the secondary ions, products
of the molecular ion decay. The fragmentation of IIIa–
IIIc molecular ions occurred majorly via simultaneous
splitting of N4–C3 and С5–N1 or of N4–C3 and N1–N2
of the triazole ring, and subsequent decay into low
molecular weight ions. In the electrospray ionization
(ESI) mass spectra of the complexes IVa and IVb,
besides the molecular ion peak, the peaks assigned to
ion-molecular associates with sodium cation and to the
fragments formed due to elimination of one of the
ligands were registered.
1
In the Н NMR spectra of IIIa–IIIc and IVa in
CDCl3, the signal of methyl group of triazole fragment
was observed at 2.09–2.53 ppm, whereas the aromatic
protons resonated at 6.52–8.16 ppm. The 13С NMR
spectra of triazoles IIIa–IIIc, contained 17 (IIIa), 18
(IIIb), and 21 (IIIc) carbon signals, including 7, 8 and
9 “quaternary” 13С signals, respectively, and were in
full accordance with the assumed structures. In the
monoresonance 13С spectra of the same compounds:
the “quaternary” С5 of triazole ring signal was ob-
served as doublet [150.67 ppm and 3JС,Н 4.4 Hz (IIIa),
Triazoles II and IIIa–IIIc were conformationally
non-rigid due to free rotation of the phenol and
benzthiazole fragments around their single bonds with
the triazole ring; that could lead to formation of
different coordination nodes and, therefore, to different
complexes structure.
3
152.50 ppm and JСН 5.0 Hz (IIIb), and 151.20 ppm
and 3JС,Н 3.7 Hz (IIIc)] due to far spin-spin interaction
with Н3' of the phenolic fragment; the signal of С3 in
triazole ring appeared as quartet [165.46 ppm and 2JС,Н
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SYNTHESIS, STRUCTURE, AND SPECTRAL LUMINESCENT PROPERTIES
2077
In order to deeper investigate the conformational
possibilities, for triazole II taken as a representative
example, by means of the DFT B3LYP/6-31G(d,p)
method we estimated the relative stability of the iso-
meric and conformational forms with varied structure
of the coordination nodes; further, we estimated the
energy barriers of their transitions via rotation around
the single bond between hydroxyphenyl and triazole
rings, as well as of the hydroxyl rotation around the
C–O bond.
According to the gas phase computations, the
structures IIa–IId corresponded to the minima at the
potential energy surface of II.
CH3
3
N2
H
4
N
O
2'
3''
N
5
S
S
H
H
3''N
N1
2''
3''N
1'
2''
2''
N1
N2
O
O
2'
N2
S
N1
5
2'
5
3
4N
3
4N
IIb
CH3
1'
1'
CH3
IIa
IIe
The rotamers IIa and IIb (formed by rotation of the
phenol and triazole rings around C1'–C5) were similar
in stability (ΔEZPE 3.0 kcal mol–1), the IIa form
corresponding to the global minimum of the potential
energy surface. The barrier ΔE≠ZPE of the IIa→IIb
transition via the intermediate state IIe was of
8.0 kcal mol–1 (Figs. 1 and 2, Table 1), that was
consistent with the presence of both rotamers with the
six-membered (IIa) and eight-membered (IIb)
coordination nodes, being in equilibrium due to fast
rotation around C1'–C5 In IIe, the rings were almost
orthogonal, the C2'C1'C5N4 torsion angle was of 96.1° .
According to the computations, the rotamer IIc
with the hydroxyl in exo position was less stable than
IIa, by ΔEZPE = 8.9 kcal mol–1.
CH3
H2'
H
H
CH3
N
CH3
N
O
O
O
N
N
N
N
2'
N
N
N
1'
S
S
S
N
N
N
IIa
IIf
IIc
The energy barrier of the (IIa)→(IIc) transition via
rotation around the С–О bond, through the IIf
intermediate was of 10.6 kcal mol–1 (Fig. 3, Table 1).
In the intermediate IIf, the hydroxyl group was off the
phenyl ring plane (torsion angle C1'C2'OH2' of 113.4°).
The latter reason should have resulted in the
possibility of hydrogen transfer from phenolic oxygen
to triazole nitrogen in IIa with formation of the isomer
IIg. However, according to the computations, IIg was
CH3
H
4
O
N
N2
Significant difference in thermodynamic stability
between IIa and IIb pair as compared with IIc was
due to formation of the stabilizing intramolecular
hydrogen bonds in IIa and IIb (Fig. 1). The calculated
energy barrier of rotation around C–O (10.6 kcal mol–1),
unexpectedly high for such process, was as well due to
stabilization of IIa by the hydrogen bonding between
hydroxyl hydrogen atom and the triazole nitrogen.
5
2'
S
3'' N
1N
2''
2''
5
O
N1
S
N2
3''N
2'
N4
CH3
H
IId
IIg
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 11 2013

2078
BELDOVSKAYA et al.
ΔEZPE = 29.5 kcal mol–1 (Table 1); thus, the hydrogen
transfer in the ground state was impossible.
Table 1. Total and relative energy of the ground state
structures of conformers and isomers of II in gas phase, and
of their intermediates [B3LYP/6-31G(d,p)a]
However, formation of the quinoid isomer IId
could be realized by the photoinitiated excited state
intramolecular proton transfer (ESIPT) from the
phenol group to the nitrogen atom of the triazole ring.
The possibility of ESIPT process in the case of II was
due to considerable increase of acidity of the phenolic
hydroxyl and the basicity of the imine nitrogen in the
triazole fragment upon excitation. That was observed
in the case of o-hydroxyphenylazoles [18, 25], struc-
turally similar to II.
ΔEZPE
,
Comp. no.
Etotal, au
ω1, cm–1
kcal mol–1
–1309.3860
–1309.3808
–1309.3708
–1309.3378
–1309.3721
–1309.3673
0b
19
29
IIа
IIb
IIc
IId
IIe
IIf
3.0
8.9
20
29.5
8.0
28
–39c
–370c
In the electronic absorption spectrum of II, the
absorption maximum of the long-wavelength band due
to π→π* transitions was observed at 286–314 nm in
polar (acetonitrile, DMSO) as well as in nonpolar
(hexane, toluene) solvents (Table 2, Fig. 4), thus
proving the existence of the benzoic structure IIa in
the solutions.
10.6
a
Etotal is total energy, 1 au = 627.5095 kcal/mol; ΔEZPE is relative
energy accounting for zero harmonic oscillations; ω1 is the
b
lowest harmonic oscillation frequency.
EZPE (IIa) =
c
–1309.1305 au. The only imaginary harmonic oscillation
frequency.
unstable and was not located at the potential energy
surface of II. The keto form IId was localized in a
local minimum, the corresponding structure had the
benzthiazolyltriazole fragment rotated by 180°, that
fragment was non-planar (torsion angle C5N1C2''N3'' of
–42.7°). The IId isomer was less stable that IIa by
In contrast to the absorption spectra, the spectra of
luminescence of solutions of II were different
depending on the solvent. In particular, in the polar
solvents II revealed the luminescence at short
f l
max
wavelength: λ = 334 nm (DMSO) or 392 nm
(CH3CN). In the nonpolar solvents the fluorescence
IIа, С1
IIb, С1
Fig. 1. Geometry parameters of IIa and IIb in gas phase and charges at atoms as computed by B3LYP/6-31G(d,p). Hereafter bond
lengths are reported in Å.
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SYNTHESIS, STRUCTURE, AND SPECTRAL LUMINESCENT PROPERTIES
2079
IIc, С1
IId, С1
Fig. 2. Geometry parameters of IIc and IId in gas phase and charges at atoms as computed by B3LYP/6-31G(d,p).
IIe, С1
IIf, С1
Fig. 3. Geometry parameters and charges of rotation intermediates IIe and IIf in gas phase as computed by B3LYP/6-31G(d,p).
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 11 2013

2080
BELDOVSKAYA et al.
Table 2. Parameters of spectra of absorbance and fluore-
scence of II–IVa
was observed, assigned to OH of phenolic fragment,
whereas NH signal of IId form should have been
found at 6–7 ppm. Furthermore, the very sharp form of
the signal also pointed at the only rotamer in the
solution. In the nonpolar solvents, the benzoid form
IIa was stabilized by strong intramolecular hydrogen
bond between phenolic hydroxyl and the triazole ring;
that favored the proton transfer to the triazole nitrogen
atom in the excited state via the ESIPT process, and
led to formation of the quinoid IId structure, emitting
in the long-wavelength region. In the polar solvents (or
in the presence of water traces in the nonpolar
solvents), the intermolecular hydrogen bond of triazole
nitrogen and the solvent (or water) was formed instead,
inhibiting the ESIPT process, thus only the short-
wavelength emission of the IIa form was observed.
The validity of that explanation was directly confirmed
by addition of small amounts of DMSO to the toluene
solution of II, accompanied by the appearance of the
short-wavelength band in the emission spectrum. With
more of the polar DMSO added, the intensity of that
band steadily increased, whereas the long-wavelength
emission was decreased (Fig. 5).
λmax, nm (ε×10–4,
λfm1ax, nm (φ)
L mol–1 cm–1)
aceto-
nitrile
aceto-
nitrile
toluene
DMSO toluene
286 535
DMSO
334
IIb
314
296
392
(1.62)
(1.27)
(1.57) (<0.001) (0.008) (0.011)
278 388 353 337
(1.21) (<0.001) (0.009) (0.013)
289 375 395 396
(1.45) (0.008) (0.011) (0.028)
296 390 398 408
(1.35) (0.025) (0.017) (0.016)
308
300
IIIa
IIIb
IIIc
IVa
IVbc
(1.71)
(1.32)
288
287
(1.18)
(1.25)
297
294
(1.26)
(1.32)
368
356
359
457
460
465
(1.40)
(1.74)
(1.66)
(0.12)
(0.31)
(0.22)
–
–
388
–
–
446
(1.57)
(0.005)
a
Fluorescence at λex = 300 nm. b In hexane, λmax = 311 nm (1.34),
λfm1ax = 540 nm (0.003). c IVb was only soluble in DMSO.
The low quantum yield of triazole II luminescence
(φ = 0.001–0.011, Table 2) was evidently due to
radiationless deactivation of its excited state via the
ESIPT mechanism. The absorption and luminescent
properties of triazoles IIIa–IIIc with the fixed benzoic
structure were in agreement with those of II, and
confirmed the occurrence of the ESIPT process. In
f l
was observed at λ
= 535 nm (toluene) or 540 nm
max
(hexane), with unusually high Stokes shift of 13155–
13635 cm–1. The excitation spectra of II in the polar
solvents were identical to the respective absorption
spectra; therefore the observed luminescence was due
to the benzoid form IIa, whereas in the nonpolar
solvents the absorption and the excitation spectra were
dissimilar. That the only form present in the solutions
particular, the absorption spectra of IIIa–IIIc (λmax
=
288–297 nm, Table 1) were similar to that of II. In the
emission spectra, independently of the solvent nature,
only the short-wavelength luminescence was observed
(λfmlax = 375–409 nm, Table 1) with ordinary Stokes
shift values (5004–9274 cm–1). The ESIPT process in
IIIa–IIIc was impossible due to the absence of mobile
protons; therefore, the long-wavelength luminescence
of II could be definitely assigned to the formation of
quinoid structure IId in the excited state.
1
without irradiation was IIa, was confirmed by Н
NMR spectrum in CDCl3: the sharp signal at 11.39 ppm
D
Intensity, rel. units
In contrast with the conformationally labile
triazoles II and IIIa–IIIc showing low quantum yield
of fluorescence, the corresponding Be complex IVa
(L2Be) revealed intense luminescence (φ 0.12–0.31) in
f l
max
the blue spectral region (λ = 457–465 nm) (Fig. 2,
Table 1), due to rigid tetrahedral configuration
preventing the radiationless deactivation of the excited
state. Thus, IVa was an efficient metal complex
luminophor, promising for application in OLEDs.
λ, nm
Fig. 4. Absorption (1–3) and fluorescence (1'–3') spectra of
II (1 and 1'), IIIb (2 and 2'), and IIIc (3 and 3') in
acetonitrile (с 2×10–5 mol/L).
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SYNTHESIS, STRUCTURE, AND SPECTRAL LUMINESCENT PROPERTIES
Even though the absorption of the copper(II) com-
2081
Intensity, rel. units
plex IVb exhibited red shift by approximately 30 nm
as compared with IVa, it revealed luminescence at the
f l
max
shorter wavelengths (λ = 446 nm) (Fig. 2, Table 2).
The low quantum yield of luminescence in the case of
IVb (φ = 0.005) was due to its paramagnetic pro-
perties, as evidenced by its effective magnetic moment
at 298 K (μef = 2.21μB, μB = 927.4009×10–26 J T–1), and
the broadened intense EPR signal (g║ = 2.073, g┴ =
2.019).
EXPERIMENTAL
λ, nm
IR spectra were recorded with Varian Excalibur
3100 FT-IR spectrometer in thin layer. 1Н NMR
(250.13 MHz) and 13С NMR (62.90 MHz) spectra in
CDCl3 were registered with Bruker DPX-250 spectro-
meter. The chloroform signals (δH 7.27 ppm and δС
77.00 ppm) were used as internal standard. The EPR
spectrum of copper(II) complex IVb was registered in
the solid state with Bruker EMXplus-10/12
spectrometer. Mass spectra were registered with
Finnigan MAT INCOS 50 unit (direct injection) or
with Finnigan LCQ Deca XP MAX unit (electrospray
ionization, ESI). Absorption spectra were recorded
with Cary Scan 100 spectrophotometer. Fluorescence
spectra were recorded with Cary Eclipse spectro-
fluorimeter. All spectral measurements were per-
formed at room temperature. The quantum yield of
fluorescence was determined with respect to aceto-
nitrile solution of anthracene according to
Fig. 5. Fluorescence spectra of triazole II (toluene, с =
2×10–5 mol/L, λex = 320 nm). (1) initial solution, (2–8) after
sequential addition of DMSO, 0.05 mL at each step.
phical representations of structures used in this
publication were prepared in GaussView 3 software
[29]. Charges at atoms were calculated following the
Mulliken population analysis.
4-Oxo-1,3-benzoxalinium perchlorate I and benz-
thiazoltriazol II were prepared according to [24] and
[11], respectively.
2-[5-(2-Metoxyphenyl)-3-methyl-1,2,4-triazol-1-
yl]-1,3-benzthiazol (IIIa). 2.3 g of Ag2O was added to
a solution of 0.31 g (1 mmol) of II in 20 mL of
chloroform, and the mixture was refluxed during
15 min. Then, 0.16 mL of methyl iodide was added,
and the mixture was further refluxed during 3 h. The
mixture was then cooled down, the inorganic
precipitate was filtered off, the mother liquor was
stripped to dryness under vacuum, and the obtained
residue was twice recrystallized from propanol-2.
Yield 0.27 g (58%), colorless crystals, mp 152–154°C.
IR spectrum, ν, cm–1: 1436, 1466, 1503, 1519 (С=С),
φ = φ0ID0/I0Dn2/n02,
where φ and φ0, quantum yields of the studied sample
fluorescence and of acetonitrile solution of anthracene,
respectively; I and I0, the integral intensities of the
respective fluorescence spectra; D and D0, respective
absorbance at the excitation wavelength; n and n0
refractive indices of the respective solutions. The
quadratic term accounting for the refractive index
difference was discussed in [25, 26]. The quantum
yields were measured in dilute solutions, with
absorbance at the excitation wavelength being in the
range of 0.10–0.12. The solvents (toluene, acetonitrile,
DMSO, hexane) were purified and dried according to
common procedures [27].
1
1567, 1593, 1623 C=N). Н NMR spectrum, δ, ppm:
2.48 s (3Н, CH3), 2.67 s (3Н, CH3), 7.19–7.45 m (6Н,
Н
arom), 7.59 t (1Н, Нarom, 3J 7.5 Hz), 8.16 d (1Н, Нarom
,
3J 7.8 Hz). 13C NMR spectrum, δC, ppm: 14.81 (СH3),
16.13 (СH3), 111.50 (Сarom), 116.86 (Сarom), 122.13
(Сarom), 125.00 (Сarom), 125.34 (Сarom), 125.86 (Сarom),
125.93 (Сarom), 127.02 (Сarom), 132.00 (Сarom), 133.69
(Сarom), 135.86 (С2''thiaz), 141.98 (Сarom), 150.67 (С5triaz),
151.30 (Сarom), 165.46 (С3triaz). Mass spectrum (EI, 70 eV),
m/z (Irel, %): 136 (55), 190 (15), 275 (50), 281 (10) [M
– CH3CN]+, 289 (13) [M – HS]+, 322 (100) [M]+.
Found, %: С 44.30; Н 3.30; N 42.40; S 6.70.
С17H14N4OS. Calculated, %: С 44.16; Н 3.03; N 42.43;
S 6.92. M 322.
The quantum-chemical computations were per-
formed via DFT with triparametric B3LYP potential in
the split-valence basis 6-31G(d,p) [28] using
GAUSSIAN-03 software package. The stationary
points were identified by Hessian calculations. Gra-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 11 2013

2082
BELDOVSKAYA et al.
{2-[2-(1,3-Benzthiazol-2-yl)-5-methyl-1,2,4-triazol-
3.90; N 12.10; S 13.80. С23H18N4O3S. Caclulated, %:
С 59.74; Н 3.89; N 12.12; S 13.87. M 462.
3-yl]phenyl}acetate (IIIb). 3 droplets of 70% HClO4
were added to a stirred suspension of 0.31 g (1 mmol)
of II in 2 mL of Ас2О. The mixture warmed up, and
the parent compound was dissolved. The mixture was
incubated during 2 days at room temperature, and then
diluted with 50 mL of water. After 1 day, the formed
precipitate was filtered off, washed with water, and
dried. The product was twice recrystallized from
cyclohexane and once from heptane. Yield 0.19 g
(54%), colorless crystals, mp 59–61°C. IR spectrum, ν,
cm–1: 1438, 1464, 1533 (С=С), 1550, 1597, 1614
(C=N), 1742, 1764 (C=O). 1Н NMR spectrum, δ, ppm:
1.85 s (3Н, CH3), 2.53 s (3Н, CH3), 7.30–7.82 m (8Н,
Bis{2-[1-(1,3-benzthiazol-2-yl)-3-methyl-1Н-1,2,4-
triazol-5-yl]phenolato}beryllium (IVa). Solution of
0.14 g (0.5 mmol) of beryllium sulfate tetrahydrate
was added to a hot solution of 0.3 g (1 mmol) of II and
0.04 g (1 mmol) sodium hydroxide in 10 mL of
methanol. The formed precipitate was boiled during 3 h,
filtered off, and twice washed with 10 mL of boiling
methanol. The complex was recrystallized from the
methylene chloride–methanol (2 : 1) and then from the
toluene – heptane (1 : 1). Yield 52%, yellow crystals, mp >
260°C. IR spectrum, ν, cm–1: 1420, 1438, 1473, 1490
(C=C), 1547, 1575, 1610 (С=N). 1Н NMR spectrum, δ,
ppm: 2.09 s (3Н, CH3), 6.52 t (1Н, Нarom, J 7.5 Hz),
7.03 d (1Н, Нarom, J 7.5 Hz), 7.32–7.65 m (4Н, Нarom),
7.96 d (1Н, Нarom, J 7.5 Hz); 8.13 d (1Н, Нarom, J 7.5 Hz).
Mass spectrum (ESI), m/z (Irel, %): 314 (23) [M – L]+,
622 (100) [M + H]+, 644 (35) [M + Na]+. Found, %: С
61.20; Н 4.00; N 10.60; Be 1.80. С32H22N8O2S2Be.
Calculated, %: С 61.64; Н 3.53; N 10.28; Be 1.44. M
621.
Н
arom). 13C NMR spectrum, δC, ppm: 14.36 (СH3),
21.20 (СH3), 121.51 (Сarom), 121.70 (Сarom), 123.06
(Сarom), 124.03 м (Сarom), 125.89 (Сarom), 126.02
(Сarom), 127.10 (Сarom), 131.85 m (Сarom), 132.12 м
(Сarom), 133.91 (Сarom), 149.49 (Сarom), 150.95 (Сarom),
152.50 (С5triaz), 156.90 (С2't'hiaz), 162.57 (С3triaz), 168.32
(С=О). Mass spectrum (EI, 70 eV), m/z (Irel, %): 148
(70), 189 (30), 291 (100) [M – CH3COO]+, 308 (64)
[MH – CH3CO]+, 309 (15) [M – CH3CN]+, 350 (7) [M]+.
Found, %: С 62.40; Н 4.50; N 15.40; S 9.40.
С18H14N4O2S. Calculated, %: С 61.72; Н 3.99; N 15.98;
S 9.15. M 350.
Bis{2-[1-(1,3-benzthiazol-2-yl)-3-methyl-1Н-1,2,4-
triazol-5-yl]phenolato}copper(II) (IVb). 0.1
g
(0.5 mmol) of copper(II) acetate monohydrate in 6 mL
of methanol was added to a hot solution of 0.3 g
(1 mmol) of II in 5 mL of methanol. The formed
precipitate was boiled during 3 h, filtered off, and
washed twice with 10 mL of boiling methanol. The
complex was recrystallized from DMSO. Yield 0.24 g
(37%), brown crystals, mp >260°C. IR spectrum, ν,
cm–1: 1439, 1470, 1507, 1533 (C=C), 1549, 1563,
1610 (С=N). Mass spectrum (ESI), m/z (Irel, %): 338
(34) [M – L]+, 646 (100) [M + H]+, 668 (27) [M + Na]+.
Found, %: С 56.40; Н 2.90; Cu 10.20; N 17.50; S
10.40. С30H22CuN8O2S2. Calculated, %: С 55.81; Н
3.40; Cu 9.84; N 17.34; S 9.91. M 645.
{2-[2-(1,3-Benzthiazol-2-yl)-5-methyl-1,2,4-triazol-
3-yl]phenyl}4-mehtylbenzolsulfonate (IIIc). 2.76 g
(4 mmol) of the freshly calcined potassium carbonate
and 0.19 g (1 mmol) of tosyl chloride were
sequentially added to a solution of 0.31 g (1 mmol) of
II in 10 mL of butanone, and the mixture was refluxed
during 3 h. After cooling down to room temperature,
20 mL of icy water was added, the formed precipitate
was filtered off and twice recrystallized from
propanol-2. Yield 0.23 g (51%), colorless crystals, mp
158–160°C. IR spectrum, ν, cm–1: 1168, 1368 (SO2),
1
1440, 1457, 1507 (С=С), 1541, 1599, 1616 (C=N). Н
ACKNOWLEDGMENTS
NMR spectrum, δ, ppm: 2.31 s (3Н, CH3), 2.38 s (3Н,
CH3), 7.07 d (2Н, Нarom, J 7.6 Hz), 7.30–7.65 m (9Н,
This work was financially supported by Russian
Foundation for Basic Research (projects nos. 11-03-
00145a and 12-03-00179a), Program of Division of
Chemistry and Materials Science of Russian Academy
of Sciences (OKh-1), and President of RF (grantn
no. NSh-927.2012.3).
Н
arom), 7.82 d (1Н, Нarom, J 5.1 Hz). 13C NMR spec-
trum, δC, ppm: 14.24 (СH3), 22.08 (СH3), 121.87 (Сarom),
122.88 (Сarom), 123.78 (Сarom), 124.16 (Сarom), 125.97
(Сarom), 126.95 (Сarom), 127.47 (Сarom), 128.31 (Сarom),
130.11 (Сarom), 131.95 (Сarom), 132.29 (Сarom), 132.50
(Сarom), 134.13 (Сarom), 145.58 (Сarom), 147.68 (Сarom),
150.85 (Сarom), 151.20 (С5triaz), 156.81 (С2''thiaz), 162.13
(С3triaz). Mass spectrum (EI, 70 eV), m/z (Irel, %): 148
(81), 189 (27), 238 (15), 291 (100) [M – TsO]+, 308
(64) [MH – Ts]+, 462 (5) [M]+. Found, %: С 59.60; Н
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