Surfactant-directed one-pot preparation of novel Ti-containing mesomaterial with improved catalytic activity and reusability

Article abstract of DOI:10.1002/aoc.4471

Titanium was incorporated in ionic liquid based periodic mesoporous organosilica to prepare a nanostructured catalyst (Ti@PMO-IL) with high activity. Procedure for the synthesis of Ti@PMO-IL was followed according the simultaneous hydrolysis and condensation of alkylimidazolium ionic liquid, tetramethoxysilane (TMOS) and tetrabutylorthotitanate (TBOT) where a surfactant template was used together with a simple acid-based catalytic aproach. N₂ adsorption isotherm of the Ti@PMO-IL was studied to measure its mean pore volume, pore size distribution and specific surface area. Diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy was applied to identify the chemical bonds present in Ti@PMO-IL. The morphology of this nanomaterial was investigated by scanning electron microscopy (SEM). Transmission electron microscopy (TEM) image was used to study mesoporosity and structure order of the catalyst. The catalytic activity of Ti@PMO-IL was then studied and found to be efficient and reusable to catalyze Hantzsch reaction.

Full text of DOI:10.1002/aoc.4471

Received: 3 April 2018
DOI: 10.1002/aoc.4471
Revised: 17 May 2018
Accepted: 24 May 2018
F U L L P A P E R
Surfactant‐directed one‐pot preparation of novel
Ti‐containing mesomaterial with improved catalytic
activity and reusability
Dawood Elhamifar1
| Omolbanin Yari1 | Shaaker Hajati2
1 Department of Chemistry, Yasouj
Titanium was incorporated in ionic liquid based periodic mesoporous
University, Yasouj 75918‐74831, Iran
2 Department of Semiconductors,
organosilica to prepare a nanostructured catalyst (Ti@PMO‐IL) with high
Materials and Energy Research Center
activity. Procedure for the synthesis of Ti@PMO‐IL was followed according
the simultaneous hydrolysis and condensation of alkylimidazolium ionic
liquid, tetramethoxysilane (TMOS) and tetrabutylorthotitanate (TBOT) where
a surfactant template was used together with a simple acid‐based catalytic
aproach. N2 adsorption isotherm of the Ti@PMO‐IL was studied to measure
its mean pore volume, pore size distribution and specific surface area. Diffuse
reflectance infrared Fourier transform (DRIFT) spectroscopy was applied to
identify the chemical bonds present in Ti@PMO‐IL. The morphology of this
nanomaterial was investigated by scanning electron microscopy (SEM). Trans-
mission electron microscopy (TEM) image was used to study mesoporosity and
structure order of the catalyst. The catalytic activity of Ti@PMO‐IL was then
studied and found to be efficient and reusable to catalyze Hantzsch reaction.
(MERC), P.O. Box 31787‐316, Tehran, Iran
Correspondence
Dawood Elhamifar, Department of
Chemistry, Yasouj University, Yasouj,
75918‐74831, Iran.
Email: d.elhamifar@yu.ac.ir
KEYWORDS
Hantzsch reaction, mesoporous organosilica‐titania, recoverable catalyst, supported ionic liquid,
Ti‐based nanocatalyst
1 | INTRODUCTION
M@PMOs prepared through co‐condensation method
are more stable due to the catalytic metal centers are
Recently, periodic mesoporous organosilicas (PMOs) with
organic fragments embedded in the silica walls have
become of high interest because of their well‐defined
ordered mesoporous structure as well as high loading
and uniform distribution of organic groups in their pore
walls.[1–4] Especially, metal‐loaded PMOs (M@PMOs)
are of more interest between chemists due to the advan-
tages of both ordered mesomaterials and supported metal
catalysts and thereby their high efficiency in catalytic
processes. The M@PMOs nanomaterials are prepared by
the treatment of metallic complexes with suitable
ligand‐containing PMOs or by the co‐condensation and
hydrolysis of PMO precursors with metal–ligand complex
in the presence of structure directing agents.[5–10] The
incorporated in the material network. However, the
M@PMOs prepared via the first approach are more active
in catalytic processes owing to better accessibility of
metallic center. More recently, several M@PMOs
(M = Mn, Pd, Au, Cu, Rh, Ru, V, etc) have been prepared
and their catalytic applications have been developed in
several organic transformations.[11] Among these,
palladium, gold and manganese based ones are more
interested due to their widespread applications in differ-
ent organic reactions such as reduction, oxidation and
coupling processes.
It is worth noting that the ionic liquids (ILs) have
unique properties such as excellent thermal and moisture
stability, high conductivity, and solvation ability for a
Appl Organometal Chem. 2018;e4471.
wileyonlinelibrary.com/journal/aoc
© 2018 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.4471

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ELHAMIFAR ET AL.
wide range of organic and inorganic compounds.
Therefore, as more recent interesting example, we have
prepared a set of ionic liquid‐based PMOs‐supported metal
complexes (M@PMO‐IL) followed by the study on their
catalytic applications in a number of organic transforma-
tions,[12–14] showing high efficiency, durability, stability
and reusability under the reaction conditions applied.
Some advantages of PMO‐IL nanomaterials in comparison
with other PMOs are their high thermal stability, excellent
catalytic efficiency and especially their ionic liquid nature
making them appealing materials for a wide range of
chemical processes. However, the main disadvantage of
the most aforementioned M@PMO catalytic systems is
the non‐chemical immobilization of metallic sources
which may cause leaching problems in some cases.
Therefore, the preparation of metallic catalysts covalently
supported by the ordered mesoporous materials is of
significant attention. Interestingly, titanium as a very
attractive and important metal has been chemically well
incorporated in the body of different nanomaterials. The
titanium‐containing materials have been extensively used
as catalyst for a wide variety of reactions due to their
unique physico‐chemical properties such as high thermal
and mechanical stability as well as excellent catalytic and
photocatalytic activities.[15–21] This noble metal has also
been well immobilized in the body of ordered mesoporous
materials and successfully applied in a number of chemi-
cal processes.[22–26] Especially, in the oxidation processes
such as oxidation of alcohols and epoxidation of alkenes,
the Ti‐loaded materials play key role. However, to the best
of our knowledge, rare reports have been presented on the
periodic mesoporous organo‐metal‐silica, in which both
titanium and organic fragments have been incorporated
into silica framework.[27–29] Hence, the preparation of
the Ti@PMOs containing active titanium sites and
effective organic functional groups with high stability, effi-
ciency and applicability in the catalytic organic reactions
is the subject of research interest.
[TBA]2[W6O19],[36] clay‐supported Ni‐nanoparticles,[37]
nano‐ZnO,[38] magnetic Fe3O4 nanoparticles,[39] MgO
nanoparticles,[40] HY zeolite[41] and Montm‐K‐10.[42] The
latter catalysts showed several advantages, such as easy
recoverability and reusability, good efficiency and high
stability under applied conditions, to the traditional ones.
However, in some of these systems, hazardous solvents
were used and considerable amounts of toxic wastes were
delivered, which are their disadvantages. Therefore, it is of
high necessary to design and prepare efficient recoverable
heterogeneous catalysts for the Hantzsch process working
under green‐media.
As a part of our efforts, to explore the utility of solid‐
supported catalysts regarding the importance of the
synthesis of heterocyclic compounds in environmental
and economic point of view, herein, a novel titanium‐con-
taining ionic liquid‐based periodic mesoporous
organosilica (Ti@PMO‐IL) having remarkable properties
is prepared and characterized. Moreover, the catalytic
application of this noble catalyst is investigated in the syn-
thesis of polyhydroquinolines through Hantzsch reaction
(Scheme 1).
2 | RESULTS AND DISCUSSION
The titanium‐containing ionic liquid‐based PMO
(Ti@PMO‐IL) was prepared by hydrolysis and co‐conden-
sation of 1,3‐bis(3‐trimethoxysilylpropyl)imidazolium
chloride,
tetramethoxysilane
(TMOS)
and
tetrabutylorthotitanate (TBOT) in the presence of pluronic
P123 as structure directing agent under acidic conditions
(Scheme 1). The chemical and structural properties of
the Ti@PMO‐IL material were investigated using several
techniques such as TEM, nitrogen adsorption–desorption,
DRIFT spectroscopy and SEM.
The TEM analysis of the Ti@PMO‐IL was performed
to verify its periodicity. As seen in Figure 1, the electrons
transmitted along with the hexagonally packed cylindri-
cal mesopores experience lower energy losses compared
to those transmitted to their walls. This successfully
confirms the ordered mesoporous structure of the
Ti@PMO‐IL material.
The SEM was used to investigate the surface morphol-
ogy and particle size of the material. This showed
uniform sling‐like particles with diameter of about 5
micrometers (Figure 2). These types of mesostructures
would be good candidates for the catalysis, chromatogra-
phy, and microelectronic applications due to their high
uniformity and density.
The nitrogen adsorption–desorption analysis of the
Ti@PMO‐IL nanomaterial illustrated an isotherm of type
IV with a hysteresis loop of type H1 indicating a sharp
On the other hand, the synthesis of the
polyhydroquinoline derivatives through Hantzsch reac-
tion has become of significant interest, because such deriv-
atives are known to have biological and different
pharmacological activities and used as vital drug in the
treatment of angina and hypertension.[30–32] Traditionally,
polyhydroquinolines were synthesized using homogenous
acid catalysts in different organic solvents with drawback
of being run at high temperature in longtime.[33] Recently,
to overcome such limitations associated with aforemen-
tioned systems, many recoverable heterogeneous catalytic
systems have been designed and applied for this
important transformation. Some of the developed systems
include Zn‐VCO3 hydrotalcite,[34] poly(4‐vinylpyridinium)
hydrogen sulfate,[35] tetrabutylammonium hexatungstate

ELHAMIFAR ET AL.
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SCHEME 1 Preparation of Ti@PMO‐
IL nanocatalyst and its application in the
synthesis of biologically active
polyhydroquinolines
FIGURE 1 TEM image of the Ti@PMO‐IL
FIGURE 2 SEM image of the Ti@PMO‐IL
capillary condensation step at approximate relative pres-
sure of 0.6, and a very sharp capillary evaporation step cen-
tered around 0.4 (Figure 3). Furthermore, it is observed
that the adsorption and desorption branches are not
exactly parallel, which indicates the ‘ink‐bottle‐like’ shape
of the pores existing in Ti@PMO‐IL nanomaterial. It is
important to note that similar adsorption–desorption pat-
tern has been reported for the ordered silicas/organosilicas
with large cage‐like mesopores.[43–45] The Brunauer–
Emmett–Teller (BET) surface area and pore volume of
the prepared material were obtained to be 584 m2/g and
0.72 cm3/g, respectively.
The Barrett–Joyner–Halenda (BJH) pore size distribu-
tion (Figure 4) showed a sharp peak with mean pore diam-
eter of 3.8 nm indicating the presence of highly uniform
mesopores in the material. It is also important to note that
a peak with low intensity observed below 2 nm is assigned
to micropores. This peak is related to penetration of

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ELHAMIFAR ET AL.
FIGURE 5 DRIFT spectrum of ordered mesoporous Ti@PMO‐IL
Si bonds are observed at 1090 and 925 cm−1. The absorp-
tion signals of C=C and C=N bonds of imidazolium ring
are observed at 1566 cm−1 and 1634 cm−1, respectively.
The absorption peaks in the range of 2900–3050 cm−1
are assigned to the C‐H stretching vibrations of aliphatic
groups. The band observed around 3100 cm−1 is attrib-
uted to unsaturated C‐H stretching vibrations. Moreover,
the broad peak appeared around 3300 cm−1 is assigned to
O‐H functional groups. These data strongly confirm the
successful incorporation and immobilization of ionic
liquid moieties in the material framework.
FIGURE 3 Nitrogen adsorption–desorption isotherms of the
Ti@PMO‐IL
After the successful characterization of the Ti@PMO‐
IL, it was employed as a heterogeneous nanocatalyst
for the one‐pot multi‐component synthesis of
polyhydroquinoline derivatives under solvent‐free condi-
tions, using substituted aldehydes, 5,5‐dimethyl‐1,3‐
cyclohexanedione (dimedone), alkylacetoacetates and
ammonium acetate substrates. The reaction of benzalde-
hyde with ethyl‐acetoacetate, dimedone and ammonium
acetate was selected as a model to investigate the effects
of different parameters on the reaction progress. The best
result was obtained by carrying out the reaction with one
molar of aldehyde, ethyl‐acetoacetate, dimedone and two
molars of ammonium acetate. The reaction did not give
the desired product in the absence of catalyst even after
6 hr (Table 1, entry 1), while in the presence of
0.1 mol% of Ti@PMO‐IL, 28% yield was obtained at room
temperature after 4 h (Table 1, entry 2). The temperature
was increased to 45 and 60°C, which resulted in 62 and
80% yields, respectively, using 0.1 mol% of Ti@PMO‐IL
nanocatalyst (Table 1, entries 3, 4) indicating the benefi-
cial effect of temperature in the reaction progress. It was
also found that the catalyst loading plays important role
in the conversion rate, the optimal value of which was
obtained in the presence of 0.2 mol% of Ti@PMO‐IL
(Table 1, entries 4–6). Next, the efficiency of the
Ti@PMO‐IL was compared to ionic liquid‐free Ti‐SBA‐
FIGURE 4 The BJH pore size distribution of the Ti@PMO‐IL
ethylene‐oxide side groups of P123 surfactant in the
organosilica matrix during material preparation.[2b] The
micropores are located in the wall of mesopores.[2b] These
results are in good agreement with TEM image showing
the well‐arranged porous structure of Ti@PMO‐IL.
The DRIFT spectroscopy of the Ti@PMO‐IL was per-
formed to get detailed information about the chemical
functional moieties of the material (Figure 5). The C‐Si
stretching vibrations are observed over the range of
700–800 cm−1. The absorption bands appeared in the
ranges 670–680 and 940–965 cm−1 can be assigned to
Ti‐O‐Ti and Si‐O‐Ti vibrations, respectively.[46,47] The
symmetric and asymmetric stretching vibrations of Si‐O‐

ELHAMIFAR ET AL.
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TABLE 1 Optimization of the reaction conditionsa
using various aldehydes, alkyl‐acetoacetates, dimedone,
and ammonium acetate. For all reactions, the work‐up
involved simply quenching with ethanol, then filtration
and recrystallization in a suitable solvent. The results
are summarized in Table 2. As shown, both electron‐
donating groups (such as Me and MeO) containing
substrates and electron‐withdrawing groups (such as Cl
and NO2) bearing aromatic aldehydes were used and
delivered the corresponding polyhydroquinolines in
high to excellent yields within short reaction times at
60°C. These data confirm the high efficacy of the
designed titanium‐based nanocatalyst for the prepara-
tion of different derivatives of biologically useful
polyhydroquinolines.
The recyclability and reusability of the Ti@PMO‐IL
nanocatalyst were also studied under applied conditions
based on the aforementioned test model (Table 3). After
each run, hot ethanol was added into reaction vessel
and the obtained mixture was filtered followed by wash-
ing the catalyst with ethanol. The recovered catalyst was
Catalyst
(mol %)
Time
(min)
Yield
(%)
Entry
Temperature
1
2
No catalyst
r.t.
r.t.
360
240
Trace
28
Ti@PMO‐IL
(0.1)
3
4
5
6
7
8
Ti@PMO‐IL
(0.1)
45
60
60
60
60
60
60
60
40
20
20
20
62
80
92
96
48
40
Ti@PMO‐IL
(0.1)
Ti@PMO‐IL
(0.15)
Ti@PMO‐IL
(0.2)
Ti@SBA‐15b
(0.2)
TiO2 (0.2)
aConditions: Benzaldehyde (1 mmol), dimedone (1 mmol), ethylacetoacetate
(1 mmol) and ammonium acetate (2 mmol).
bSanta Barbara Amorphous (SBA).
TABLE 3 Recyclability of the catalyst in the Hantzsch reaction
15 and TiO2 heterogeneous catalysts with the same Ti
loading and conditions. Interestingly, the latter catalysts
delivered low to moderate yields of the desired products
under the same conditions and time as Ti@PMO‐IL
(Table 1, entry 6 versus entries 7, 8). These observations
successfully confirm the valuable role of ionic liquid
moieties in the reaction progress.
Time
(min)
Yield
(%)
Time
(min)
Yield
(%)
Run
Run
1
2
3
4
5
20
20
24
28
28
96
95
94
95
92
6
7
30
33
33
35
35
90
90
88
86
85
8
9
After the reaction conditions were optimized, the sub-
strate scope and versatility of the catalyst were examined
10
TABLE 2 Ti@PMO‐IL‐catalyzed four‐component Hantzsch reaction for the synthesis of polyhydroquinolinesa
Entry
R1
R2
Product
Time (min)
Yield/ %b
M. p. [°C]
1
2
3
4
5
6
7
8
9
Ph
Et
5a
5b
5c
5d
5e
5f
20
35
35
20
26
25
35
35
15
96 0.7
88 0.9
87 0.7
206–208
202–206
242–246
250–253
260–263
266–271
211–213
237–239
238–240
2‐Cl‐Ph
Et
2,4‐Cl‐Ph
Ph
Et
Me
Me
Me
Me
Me
Me
95
93 0.8
93
1
4‐MeO‐Ph
4‐Me‐Ph
2,4‐Cl‐Ph
3‐OEt,4‐OH‐Ph
4‐NO2‐Ph
1
5 g
5 h
5i
85 0.8
86 0.7
95 0.9
aReaction conditions: Aldehyde 1 (1 mmol), alkyl‐acetoacetate (1 mmol), dimedone (1 mmol), ammonium acetate (2 mmol). Ti@PMO‐IL (0.2 mol %), 60 °C.
bIsolated yield.

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ELHAMIFAR ET AL.
applied in the next runs. The results showed that it could
be recovered and reused at least for nine times without
notable reduction in its performance. A hot filtration test
was next performed. For this, after the progress of about
40% of the reaction, hot ethanol was added and the
obtained mixture was immediately filtered followed by
the removal of solvent and allowing the reaction of
residue to be continued at 60°C. After 1 hour, a further
conversion of only 5% was observed. The catalyst‐free
filtrate was also analyzed by atomic absorption and the
result showed no existence of titanium species in this
solution. These results proved strong durability of the
chemically‐supported Ti‐based catalyst and also con-
firmed that it operates in a heterogeneous pathway.
aldehyde (1 mmol), dimedone (1 mmol), ammonium ace-
tate (2 mmol) and methyl/ethylacetoacetate (1 mmol) in
the presence of 0.2 mol% Ti@PMO‐IL nanocatalyst. The
mixture was stirred at 60°C and the reaction progress
was monitored by TLC. After the reaction was completed,
it was stopped followed by the addition of 10 ml of hot
EtOH. The obtained mixture was hotly filtered and the
catalyst was separated. Then, some ice species were
added into filtrate to precipitate or crystallize the desired
products. The pure products were obtained after the
recrystallization of crude ones in EtOH.
4 | CONCLUSION
In summary, a novel concept for the preparation, charac-
terization and application of Ti‐containing ionic liquid‐
based PMO (Ti@PMO‐IL) was developed. The nitrogen
adsorption–desorption analysis and transmission electron
microscopy showed that the prepared material is
mesostructure and highly ordered. In addition, the SEM
image illustrated the uniform sling‐like particles for the
Ti@PMO‐IL. The DRIFT spectroscopy confirmed the
successful incorporation and/or immobilization of ionic
liquid and titanium moieties in this mesostructure. Next,
Ti@PMO‐IL was successfully applied in the preparation
of biologically active polyhydroquinolines through
Hantzsch reaction under solvent free conditions, which
resulted in the corresponding products with excellent
yield and selectivity. The catalyst was recovered several
times and reused without significant decrease in
efficiency. In fact, this methodology effectively combined
the advantages of ionic liquids, ordered mesoporous
3 | EXPERIMENTAL SECTION
3.1 | General procedure for the
preparation of the Ti@PMO‐IL
The Ti@PMO‐IL was prepared by the simultaneous hydro-
lysis and condensation of 1,3‐bis(3‐trimethoxysilylpropyl)
imidazolium chloride ionic liquid (IL), tetramethoxysilane
(TMOS) and tetrabutylorthotitanate (TBOT) in the pres-
ence of P123 surfactant under acidic conditions. The pro-
cedure of Ti@PMO‐IL synthesis is typically follows as:
pluronic P123 (1.5 g) and KCl (8 g) were added to a solution
containing 9.5 g of distilled water and 41.6 g of HCl (1.4 M)
under stirring at 35°C. After a homogeneous solution was
prepared, a mixture of 1,3‐bis(3‐trimethoxysilylpropyl)
imidazolium chloride (1.8 mmol) and tetramethoxysilane
(14 mmol) was added and stirred for 45 min. Next, 5 mmol
of TBOT was added drop‐wise and the resulting mixture
was stirred for 24 h while keeping the same temperature.
The obtained mixture was transferred into a Teflon‐lined
autoclave and heated at 100°C for 72 hr under static
conditions. After cooling the reaction mixture to room
temperature, it was filtered and completely washed with
ethanol and deionized water. The block co‐polymer P123
was extracted by acidic ethanol using Soxhlet apparatus.
The obtained powder was dried at 70°C for 12 hr under
vacuum and denoted as Ti@PMO‐IL. By using the induc-
tively coupled plasma atomic emission spectroscopy
(ICP‐AES) the loading of Ti was calculated.
materials,
solvent‐free
media
and
chemically‐
immobilized metal catalysts for the easy separation of
products and the recycling of catalyst. According to the
aforementioned advantages of the present catalyst, some
of its applications in other organic processes are under-
way in our laboratories.
ACKNOWLEDGMENTS
The authors thank the Yasouj University and the Iran
National Science Foundation (INSF) for supporting this
work.
3.2 | General procedure for the synthesis
of polyhydroquinolines through Hantzsch
reaction using Ti@PMO‐IL nanocatalyst
CONFLICTS OF INTEREST
There are no conflicts of interest to declare.
The synthesis of polyhydroquinolines was performed
assisted by a magnetic stirrer in a round‐bottom flask
fitted with a condenser and placed in a temperature con-
trolled oil bath. Typically, the flask was charged with
ORCID
Dawood Elhamifar http://orcid.org/0000-0003-4889-9505

ELHAMIFAR ET AL.
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Elhamifar, M. Nasr‐Esfahani, B. Karimi, R. Moshkelgosha, A.
Shabani, ChemCatChem 2014, 6, 2593.
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How to cite this article: Elhamifar D, Yari O,
Hajati S. Surfactant‐directed one‐pot preparation of
novel Ti‐containing mesomaterial with improved
catalytic activity and reusability. Appl Organometal
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