IR-Spectroscopic Study of Adsorption of Aminoazoles on Oxide Catalysts of Biginelli Reaction

Article abstract of DOI:10.1134/S0023158418020106

Adsorption of 5-aminotetrazole and 3-aminotriazole on the surface of nanosized oxides of Al and Si–Ti, which are catalysts of the Biginelli reaction with the participation of aminoazoles, have been studied using the method of IR spectroscopy. It has been

Full text of DOI:10.1134/S0023158418020106

ISSN 0023-1584, Kinetics and Catalysis, 2018, Vol. 59, No. 2, pp. 188–195. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © O.V. Koryakova, Yu.A. Titova, A.N. Murashkevich, O.V. Fedorova, 2018, published in Kinetika i Kataliz, 2018, Vol. 59, No. 2, pp. 215–223.
IR-Spectroscopic Study of Adsorption of Aminoazoles on Oxide
Catalysts of Biginelli Reaction
O. V. Koryakovaa, Yu. A. Titovaa, A. N. Murashkevichb, and O. V. Fedorovaa, *
aInstitute of Organic Synthesis, Ural Branch, Russian Academy of Sciences, Yekaterinburg, 620990 Russia
bBelarusian State Technological University, Minsk, 220006 Belarus
*e-mail: fedorova@ios.uran.ru
Received November 15, 2016; in final form, August 23, 2017
Abstract⎯Adsorption of 5-aminotetrazole and 3-aminotriazole on the surface of nanosized oxides of Al and
Si–Ti, which are catalysts of the Biginelli reaction with the participation of aminoazoles, have been studied
using the method of IR spectroscopy. It has been shown that 5-aminotetrazole and 3-aminotriazole interact
with the Brønsted base centers on the oxide surface, with the behavior of aminoazole in the Biginelli reaction
being determined by the coordination.
Keywords: IR spectroscopy, Biginelli reaction, catalysts, nanosized oxides of metals and silicon, aminoazoles,
adsorption
DOI: 10.1134/S0023158418020106
Metal oxides are widely used as catalysts in organic tion of aldehyde (I), a CH-active compound (II), and
synthesis both in industry and in laboratory practice an NH-active compound, which is urea (IIIa),
[1]. Review [2] considered the applications of oxides thiourea (IIIb) [3] or aminoazoles (IVa and IVb) [4].
of metals and silicon in the condensation reactions, Substituted dihydroazolo[1,5-a]pyrimidines of type
reactions with the formation of C–N and C–O bonds VIa and VIb, which are of interest as distant analogues
and in multicomponent reactions. The latter includes of purines and nucleosides, possess a wide spectrum of
the Biginelli reaction (Scheme 1) with the participa- biological activities [5–7].
EtO2C
N
*
NH2
X
IIIa, b
H2N
Me
N
H
X
Va, b (X = O, S)
O
O
HN
N
Y
+
H2N
N
EtO
Me
O
H
IVa, b
EtO2C
*
N
N
Y
I
II
Me
N
H
N
VIa, Y = N; VIb, Y = CH
Scheme 1. The Biginelli reaction.
The catalysts for the classical Biginelli reaction, [9], InCl3 [10], LaCl3 ⋅ 7H2O [11], lanthanides or cop-
which involves urea or thiourea, are well known.
These are mineral and Lewis acids (e.g., BF3–OEt2) in
combination with salts of transition metals [8], FeCl3
per triflate [12, 13]. Sometimes, this reaction is carried
out in the presence of metal oxides: aluminum oxide
supported on molybdenum oxide [14], palladium
188

IR-SPECTROSCOPIC STUDY
189
Table 1. The influence of the nature of the catalyst and solvent on the yield of compound VIa at 22–23°C (according to
HPLC data)
Reaction
time
Ssp, m2/g
No. Order of reagent loading
Catalyst
−
Solvent
Yield VIа, % Yield VII, %
1
2
3
4
5
6
7
–
–
EtOH
CH3CN
<3
<3
8
<3
<3
<3
<3
4
40 h
–
–
12
20
5
Morpholine
CF3COOH
SiO2
–
–
<3
<3
<3
<3
<3
<3
<3
<3
4
266
46
0.2
I + II + IVа
8
ZnO
<3
5
Al2O3
9
197
250
394
179
279
THF
7 days
TiO2
10
4
11
MgO
15
12
18
20
25
SiO2–ZrO2
SiO2–MgO
SiO2–TiO2
SiO2–TiO2
12
13
14
220
15 I + II, after 30 min + IVа
9
oxide [15], or nanosized zirconium oxide [16]. We oxides, which contain active centers of different
have studied nanosized oxides of aluminum, copper, natures [18–25], was investigated by IR spectroscopy.
zinc, and titanium as catalysts in the Biginelli reaction These results were used to explain the different behav-
[17]. It has been shown that the observed increase in ior of aminoazoles in the Biginelli reaction, as well as
the reaction chemoselectivity is associated with activa- the different catalytic activity of oxides Al2O3 and
tion of benzaldehyde (I), acetoacetic ester (II) and
urea (IIIa) under conditions of their sorption on the
surface of nanosized oxide catalyst [17, 18].
SiO2–TiO2 in this reaction.
Substituted dihydroazolo[1,5-a]pyrimidines of
type VIa and VIb are mostly synthesized under heating
(90–150°C) using mineral or organic acids (e.g., sul-
famic [19] or toluensulfonic acid [20]), N,N,N,N-
tetrabromobenzene-1,3-disulfonamide [21], as well as
Lewis acids [19] as catalysts. Only one work is known [22]
in which the compound VIb was synthesized at room
temperature using ionic liquid [Bmin]BF4 as a catalyst.
The search for new catalysts that allow the synthe-
sis of substituted dihydroazolo[1,5-a]pyrimidines
without heating is an important problem, since such
catalysts can be useful in the development of stereose-
lective methods of synthesis [23]. Stereoselective syn-
thesis of compound Va at a room temperature in the
presence of nanooxides Al2O, SiO2–TiO2 and SiO2–
ZrO2 was described in [24, 25].
MATERIALS AND METHODS
Reagents
Reagents produced by Lancaster were used in the
experiments, including urea (99%), benzaldehyde
(99%), 5-aminotetrazole monohydrate (97%), anhy-
drous 3-aminotriazol (98%), and acetoacetic ester
(99%, Acros Organics).
Synthesis of Catalysts
Individual nanosized oxides of titanium, silicon,
aluminum, zinc, and magnesium were prepared by the
sol–gel method [26]. Double nanooxides SiO2–ZnO2
(3 : 1), SiO2–MgO (3 : 1) and SiO2–TiO2 (3 : 1) were
In the present work, we studied catalysts for the prepared in a similar way by mixing sols at a predeter-
synthesis of dihydroazolopyrimidines VIa and VIb at mined ratio with subsequent drying at 100–150°C to
room temperature. The sorption of aminoazoles IVа constant mass. The values of the specific surface area
and IVb on the surface of Al2O3 and SiO2–TiO2 nano- (Ssp) of the studied samples are given in Table 1.
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190
KORYAKOVA et al.
Methods for Analysis of Catalysts
The melting points were measured using a Boetius
Study of the Catalytic Action of Nanooxides
in the Biginelli Reaction
heating microstage (Germany) without further adjust-
ment of the results. Diffuse reflectance spectra of the
samples in the powder state were recorded on a Spec-
trum One IR-Fourier spectrometer (Perkin Elmer,
United States) equipped with an automatic diffuse
reflectance attachment. The diffuse reflectance spec-
trum was converted to Kubelka–Munch units using
Spectrum software. The addition of the spectra was
performed using the Speсtral Calсulator program
implemented in Spectrum, which allows estimation of
the contribution of each component in the spectral
picture. The 1H NMR spectra were recorded using an
AVANCE DRX-400 spectrometer (Bruker, Germany)
with an operating frequency of 400.13 MHz (internal
standard TMS). The elemental analysis was carried
out on an EA 1108 CHN-analyzer (Carlo Erba Instru-
ments, Italy).
The Biginelli reaction was carried out in a tetrahy-
drofuran (THF) with a molar ratio of aldehyde : aceto-
acetic ester (AAE) : aminoazole : metal nanooxide =
1 : 2 : 1 : 0.1. The reaction mass was stirred at a tempera-
ture of 22–25°С for 7 days and then was evaporated.
The obtained crude product was analyzed by
1H NMR and high-performance liquid chromatogra-
phy (HPLC) on an Agilent 1200 chromatograph (Agi-
lent Technologies, USA, a Chiralpak AD-H column
(Daicel Chemical Industries, Japan), the eluent
CH3CN–H2O (35 : 65), at a wavelength of 285 nm).
The contents of target compound VI and chalcone VII
(Scheme 2) in the reaction mass were determined
according to the HPLC data on the same column
using the method of absolute calibration.
HN
H2N
IVa
N
N
+
N
EtO2C
Me
EtO2C
Me
O
O
O
H
N
N
N
+
EtO
Me
I
N
H
N
O
II
VIa
VII
Scheme 2. Products of the Biginelli reaction with the participation of 5-aminotetrazole.
Study of the Adsorption of Aminoazoles
We also studied the influence of the nature of
nanosized oxides (SiO2, Al2O3, ZnO, MgO, TiO2,
SiO2–ZrO2, SiO2–MgO, SiO2–TiO2 ) on the yield of
products. These oxides have a high specific surface
area (from 46 to 394 m2/g) and contain particles rang-
ing in size from 10 to 80 nm. It turned out that in the
presence of MgO, the reaction proceeds more selec-
tively than in the presence of SiO2, ZnO, TiO2 and
Al2О3 (compare nos. 7–10 and 11 in Table 1). The best
results were achieved using mixed nanooxides SiO2–
MgO and SiO2–TiO2.
Adsorption of aminoazoles on nanooxides of
metals or silicon was carried out from methanolic
solutions of the sorbate (at the sorbate : sorbent molar
ratio of 1 : 3) followed by removal of the solvent.
RESULTS AND DISCUSSION
Similar to the classical Biginelli reaction (synthesis
of compounds Va and Vb), which does not occur at
room temperature in the absence of a catalyst [27],
benzaldehyde (I), AAE (II) and 5-aminotetrazole
(IVа) according to the 1H NMR and HPLC data prac-
tically do not interact among themselves at 22–23°C
during a reaction time of 40 h (Table 1, no. 1). Replac-
ing the ethanol and acetonitrile solvents with tetrahy-
drofuran results in a increase of VIa yield up to 8%
(Table 1, no. 2 and 3). Some further increase in the
product yield is observed with an increase of the reac-
tion time from 40 h to 7 days (Table 1, no. 4). The reac-
tion mass always contains the intermediate chalcon
VII, which is produced by the interaction of benzalde-
hyde with AAE. If CF3COOH is replaced by morpho-
line, the yield of VIa increases to 20% (Table 1, no. 5).
A delay in adding aminoazole IVа for 30 min
increases the yield of VIa up to 25%. Therefore, SiO2–
TiO2 can be recommended as a catalyst for the stereo-
selective synthesis of compound VIa.
Dihydrotriazolopyrimidine (VIb) is practically not
formed under the conditions of multicomponent syn-
thesis at room temperature in THF in the absence of
catalysts (Scheme 3). The main product is triazolotet-
rahydropyrimidine (VIII). The reaction is stopped at
this stage and the cleavage of the water molecule does
not occur [28]. A similar result is also observed in the
presence of nanooxides Al2O3 or SiO2–TiO2.
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IR-SPECTROSCOPIC STUDY
191
O
H
HN
H2N
IVb
N
EtO2C
Me
+
N
N
EtO2C
N
N
+
N
I
N
H
N
HO
Me
N
H
N
O
O
VIII
VIb
EtO
Me
II
Scheme 3. Products of the Biginelli reaction with participation of 3-aminotriazole.
Thus, at room temperature nanosized SiO2–TiO2 the vibrations of the tetrazole ring. In addition, the
rocking vibrations of NH2 groups also contribute to
catalyzes the Biginelli reaction with the participation
of 5-aminotetrazole (Table 1, no. 14) and don’t cata- these vibrations. The position and relative intensity of
lyzes the same reaction with the participation of 3- the observed bands mostly coincide with data of [31].
The band at 1298 cm–1 was assigned to vibrations of
the N–N=N group (by analogy with the findings of
[31, 32]). A large number of bands in the region of the
stretching vibrations of NH2 (3478 and 3368 cm–1) and
aminotriazole (Table 2, no. 5).
To clarify the causes of the different behaviors of
aminoazoles in interaction with benzaldehyde and
AAE, and also different catalytic activities of nano-
sized Al2O3 and SiO2–TiO2, we studied the sorption of
5-aminotetrazole and 3-aminotriazole on the surface
of nanosized Al2O3 and SiO2–TiO2 by IR-spectros-
copy.
It is known that Lewis acid sites of nanosized
oxides of metals and silicon are positively charged
metal (silicon) atoms, whereas the Brønsted acid sites
are the hydrogen atoms of the OH groups. In turn, the
Brønsted base sites are the oxygen atoms of nanooxide
and carboxylate groups of carbon dioxide sorbed on
the catalyst surface [29].
NH groups (3338 cm–1) and the presence of the split
band of the deformation vibrations of the NH2 groups
(1640 and 1661 cm–1) indicate the existence of an
amino-imino tautomeric equilibrium [33], which is
not observed using the methodology described in [31]
for the preparation of samples in tablets with KBr.
The interaction of 5-aminotetrazole monohydrate
with aluminum nanooxide results in disappearance
of the absorption bands related to the oxoniym ion
because the oxide takes a water molecule from 5-ami-
notetrazole (Fig. 1, spectrum 2). Absorption bands
that correspond to the stretching vibrations of NH-
and NH2 groups are clearly visible against the back-
ground of the water stretching vibration band of
nanooxide at 3484 cm–1; in comparison with the
spectrum of initial 5-aminotetrazole, the number of
these bands decreases upon sorption. The absorption
bands that correspond to the deformation vibrations of
amino groups become more narrow and the band of
the NH groups shift from 1590 to 1601 cm–1. At the
same time, the bands of the tetrazole ring exhibit sig-
nificant changes: the 1064 cm−1 band splits into two
(1068 and 1049 cm−1) and the bands at 1158 and
1298 cm−1 shift to 1143 to 1265 cm−1, respectively.
These changes have been observed earlier in IR-spec-
troscopic studies of dihydrated 5-aminotetrazole [34].
The splitting and shift of the bands of the tetrazole
cycle indicate a distortion of the molecule [35]. On the
other hand, the observed changes of the spectral char-
acteristics of aluminum oxide concern only the
absorption band of carboxylate groups which is
formed upon due to the sorption of CO2 from the air
According to the elemental analysis data, 5-amino-
tetrazole (IVа) is a monohydrate. Its IR spectrum
(Fig. 1, spectrum 1) indicates the presence of the
hydroxonium ion Н3О+, as evidenced by a fairly
intense absorption in the 2768–2502 cm–1
(
)
Н3О+
ν
range and at 1781 cm–1
(
) [30]. This indicates
as,H3O+
δ
considerable acidity of the NH group of the ring.
According to the calculation results [31], absorption
bands at 1450, 1158, 1064 and 996 cm–1 are related to
Table 2. The influence of the nature of the catalyst on the
yield of compound VIb at 22–23°C in the THF environ-
ment (according to 1H NMR data)
No.
Catalyst
Yield VIb, % Yield VIII, %
1
2
3
4
5
−
CF3COOH
Morpholine
Al2O3
Traces
Traces
10
Traces
Traces
40
48
8
5
on the oxide surface: the 1419 and 1465 cm−1 bands
disappear and a band at 1451 cm−1 appears. This may
SiO2–TiO2
20
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KORYAKOVA et al.
Kubelka–Munch units
1
2
3
4000 3500 3000 2500 2000 1800 1600 1400 1200 1000 800 600
Wavenumber, cm–1
Fig. 1. The IR spectra of (1) monohydrate of 5-aminotetrazole, (2) monohydrate of 5-aminotetrazole sorbed on aluminum nano-
oxide, and (3) aluminum nanooxide.
indicate that the sorption of 5-aminotetrazole occurs tion of the stretching and deformation vibrations of
by coordination of the NH group of the tetrazole ring
mainly on the oxygen atoms of carboxylate groups of
carbon dioxide (Scheme 4, A).
The sorption of 5-aminotetrazole on the surface of
the SiO2–TiO2 composite also leads to destruction of
the oxoniym ion. In addition, the splitting of the bent system than in the initial aminoazole. This is con-
deformation vibration band of the NH2 group disap-
amino groups imply that the equilibrium is shifted
towards the tautomeric amine form and that the
NH2 group interacts with the surface of the composite
at a higher energy of the complex system of intermo-
lecular hydrogen bonds (IMHB) in the sorbate–sor-
firmed by the changes in the oxide spectrum: the shift
of Si–O–Ti and Si–O–Si bands (from 1068 and 947
to 1082 and 955 cm–1, respectively), which may be due
to the interaction of the oxygen atom in these groups
with 5-aminotetrazole (Scheme 4, A). Upon the coor-
dination of the NH2 group with the surface of the
composite, the NH group of the ring remains free,
which allows its participation in the Biginelli reaction
pears: instead of the doublet at 1641 and 1668 cm−1
there is only one band at 1651 cm–1. The spectrum also
shows a band at 1454 cm–1 related to the vibrations of
the tetrazole cycle, the remaining bands of this cycle
are not seen against the background of the absorption
of the composite. In the region of the stretching vibra-
tions of N–H bonds (3500–3000 cm–1) the number of
bands decreases (Fig. 2). Such changes in the absorp- (Scheme 4, B).
N
N
N
N
N
N
δ−
δ+
N
N
N
N
N
H
NH2
N
H
NH2
H
HN
O
C
O
C
H
Si O Ti
(HO)2Al O
O Al(OH)2
(HO)2Al O
O Al(OH)2
A
B
Scheme 4. The proposed coordination of 5-aminotetrazole on nanooxides Al2O3 (A) and SiO2–TiO2 (B).
Thus, the manner of 5-aminotetrazole coordina- xides is different: in the first case, the proton of the
tion on the surface of Al2O3 and SiO2–TiO2 nanoo-
NHgroup of the tetrazole cycle interacts with the sur-
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IR-SPECTROSCOPIC STUDY
Kubelka–Munch units
193
1
2
3
3500 3000 2500 2000
1500
1000
500
Wavenumber, cm–1
Fig. 2. The IR spectra of (1) dihydrate of 5-aminotetrazole, (2) dihydrate of 5-aminotetrazole sorbed on SiO –TiO nanooxide,
2
2
and (3) SiO –TiO nanooxide.
2
2
face, while in the second case it is the proton of the correspond to the stretching vibrations of a strongly
NH2 group. Correspondingly, in the first case the
NH group is blocked, while in the second case it is free.
This explains the effectiveness of SiO2–TiO2 nanooxide
in contrast to Al2O3 nanooxide in the Biginelli reaction
with the participation of 5-aminotetrazole.
associated NH group (Fig. 3). The absorption band at
1639 cm–1 is due to the deformation vibrations of the
NH2 group. The band at 1593 cm–1 corresponds to the
vibrations of the C=N bond of the triazole cycle, while
the bands due to vibrations of the five-membered cycle
are below 1400 cm–1 [36]. Apparently, the formation
of IMHB of the NH…N type with high energy is char-
The IR spectrum of 3-aminotriazole (which,
according to the elemental analysis data, is anhydrous)
in the 2725–2771 cm–1 range shows the bands that acteristic for 3-aminotriazole (Scheme 5, A).
N
N
N
H
N
N
N H
NH2
N
H
N
N H
NH2
N
N H
NH2
N
N H
NH2
N
N
N
N
N
H
N
N
NH2
NH2
− N
H
N
N
A
B
N
NH2
NH2
+
Scheme 5. The proposed coordination of 5-aminotriazole due to the formation of IMHB in (A) the absence and (B)
presence of nanooxide SiO2–TiO2.
When 3-aminotriazole is sorbed on aluminum after the sorption of 3-aminotriazole. The absorption
oxide (Fig. 3), absorption bands in the 1419–1445 cm–1
region, which correspond to the vibrations of carboxy-
bands due to the deformation of NH bonds of triazole
are superimposed on the deformation bands of water
late groups of the oxide, disappear; this suggests that in the 1500–1650 cm–1 range, and the sorption practi-
these groups are replaced by the sorbate interacting cally does not affect the shape of the spectrum. This
with the oxygen atoms of the surface.
indicates that the system of strong IMHB is preserved.
It can be assumed that 3-aminotriazole molecules are
adsorbed physically and settle in a flat manner on the
surface of Al2O3.
The absorption bands that correspond to the
stretching vibrations of NH and NH2 groups are seen
against the background of the broad band at 3350 cm–1
due the stretching vibrations of water of nanooxide.
The 3-aminotriazole molecules settle in a similar
The NH and NH2 bands practically do not change way in the case of sorption on the surface of SiO2–
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KORYAKOVA et al.
Kubelka–Munch units
1
2
3
4000 3500 3000 2500 2000
1500
1000
500
Wavenumber, cm–1
Fig. 3. The IR spectra of (1) 3-aminotriazole, (2) 3-aminotriazole sorbed on Al O nanooxide, and (3) nanooxide of aluminium.
2
3
Kubelka–Munch units
1
2
3
3500 3000 2500 2000
1500
1000
500
Wavenumber, cm–1
Fig. 4. The IR spectra of (1) 3-aminotriazole, (2) 3-aminotriazole sorbed on SiO –TiO nanooxide, and (3) SiO –TiO nanooxide.
2
2
2
2
TiO2 composite (Fig. 4). In contrast to the sorption on tautomeric imine form (Scheme 5, B). The maxima of
the absorption bands that correspond to the vibrations of
theSi−O−SiandSi−O−Tibondsareshiftedfrom1068to
1057 cm–1 and from 947 to 951 cm–1, respectively. The O
atoms of these are apparently involved in the sorption of
3-aminotriazole.
Al2O3, the IMHB system is somewhat disturbed. This
conclusion is supported by the decrease in the inten-
sity of the bands in the 2700–3000 cm–1 region and by
the redistribution of the intensities of the bands due to
the stretching vibrations of N−H bonds in the 3408–
3335 cm‒1 range, which can be seen against the back-
ground of the band of water of nanooxide at 3350 cm–1.
Thus, the different catalytic activities of Al2O3 and
SiO2–TiO2 nanooxides in the Biginelli reaction with
the participation of 5-aminotetrazole may be
explained by the feature of the coordination of 5-ami-
notetrazole molecule on the surface. On the surface of
Al2O3 5-aminotetrazol is coordinated by the NH
The band that appears at 1690 cm–1 should be
+
assigned to the vibrations of exocyclic C=
of the
NH2
tautomeric imine form [36–38], i.e., one part of the
molecules is in the amine form and the other part is in the
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IR-SPECTROSCOPIC STUDY
195
Ermakov, AE., Rusinov, G.L., and Charushin, V.N.,
group of tetrazole cycle, which is accompanied its pas-
sivation, whereas on the SiO2–TiO2 surface it is coor-
dinated by the NH2 group; thus, the NH group of ami-
noazole remains free and can participate in the reac-
tion. The 3-aminotriazole molecules settle in a flat
manner on the surface of Al2O3 and SiO2–TiO2 nano-
oxides and are bound with each other by IMHB,
which constrains the participation of the NH group of
the tetrazole cycle in the reaction. This explains the
lack of catalytic activity of Al2O3 and SiO2–TiO2
nanooxides in the Biginelli reaction with the partici-
pation of 3-aminotriazole.
The results of the present study of the IR spectra of
sorbed aminoazoles IVа and IVb allow us to recom-
mend nanosized SiO2–TiO2 (3 : 1) as a promising cat-
alyst for the Biginelli reaction with the participation of
5-aminotetrazole at room temperature.
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ACKNOWLEDGMENTS
This work was supported by the Presidium of the
Ural Branch of the Russian Academy of Sciences
(project 15-21-3-6) and RFBR (grant no. 16-29-
10757-ofi_m).
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Translated by V. Alekseev
nikova, I.G., Grishakov, A.N., Uimin, M.A., Mysik, A.A.,
KINETICS AND CATALYSIS Vol. 59 No. 2 2018