Phenylene and Isatin Based Bifunctional Mesoporous Organosilica Supported Schiff-Base/Manganese Complex: An Efficient and Recoverable Nanocatalyst

Article abstract of DOI:10.1007/s10562-019-02653-6

A novel bifunctional periodic mesoporous organosilica supported isatin-Schiff-base/manganese complex [BPMO@ISB/Mn(II)] is prepared, characterized and its catalytic performance is investigated in the synthesis of dihydropyrano[3,2-c]chromene derivatives. T

Full text of DOI:10.1007/s10562-019-02653-6

Catalysis Letters
https://doi.org/10.1007/s10562-019-02653-6
Phenylene and Isatin Based Bifunctional Mesoporous Organosilica
Supported Schiff-Base/Manganese Complex: An Efficient
and Recoverable Nanocatalyst
Meysam Norouzi1 · Dawood Elhamifar1
Received: 9 June 2018 / Accepted: 4 January 2019
© Springer Science+Business Media, LLC, part of Springer Nature 2019
Abstract
A novel bifunctional periodic mesoporous organosilica supported isatin-Schiff-base/manganese complex [BPMO@ISB/
Mn(II)] is prepared, characterized and its catalytic performance is investigated in the synthesis of dihydropyrano[3,2-c]
chromene derivatives. The BPMO@ISB was prepared via grafting of 3-aminopropyltrimethoxysilane (APTS) on a phe-
nylene based PMO followed by treatment with isatin. The BPMO@ISB was then reacted with Mn(NO3)2·4H2O to afford the
BPMO@ISB/Mn(II) nanocatalyst. This catalyst was characterized using Fourier transform infrared (FT-IR) spectroscopy,
thermal gravimetric analysis (TGA), energy-dispersive X-ray (EDX) spectroscopy, scanning electron microscopy (SEM), low
angle powder X-ray diffraction (LAPXRD) analysis and transmission electron microscopy (TEM). The BPMO@ISB/Mn(II)
nanocatalyst was successfully used in one-pot synthesis of 3,4-dihydropyrano[c]chromene derivatives at room temperature.
In addition, the stability, recyclability and reusability of designed nanocatalyst were studied under applied conditions.
Keywords Bifunctional PMO · Supported isatin · Schiff-base · Manganese nanocatalyst · Dihydropyrano[3,2-c]chromenes
Extended author information available on the last page of the article
Vol.:(0123456789)
1 3

M. Norouzi, D. Elhamifar
Huntington’s disease, Down’s syndrome, schizophrenia
and myoclonus [61–63]. Although several methods have
been reported for the synthesis of dihydropyrano[3,2-c]
chromenes using different catalytic systems, however,
some of these protocols suffer from disadvantages of
expensive homogenous catalyst, long reaction time,
toxic solvent, product separation and catalyst recov-
ery. Therefore, many efforts are being made to develop
green and efficient catalytic system for the synthesis of
dihydropyrano[3,2-c]chromene.
1 Introduction
Due to problems associated with chemical wastes and
environmental pollution, the goal of science has recently
shifted to design of green chemical processes to reduce
and/or remove polluting agents and therefore save envi-
ronment. One of significant and attracted idea in this mat-
ter is replacing of homogeneous catalytic systems with
their heterogeneous counterparts [1, 2]. To date a lot of
chemical and physical strategies have been developed for
immobilization of homogeneous catalysts onto solid sup-
ports such as carbon, metal oxides, mesoporous materials,
organic–inorganic hybrid materials and polymers [3–7].
Especially, periodic mesoporous organosilicas (PMOs)
have emerged as excellent support because of their excel-
lent properties such as high surface area, high capacity
for catalyst immobilization, high lipophilicity, high ther-
mal and mechanical stability and uniform distribution
of organic and inorganic moieties in their framework [2,
8–13]. These characteristics made PMOs as powerful
candidate for a lot of applications in areas of adsorption,
catalysis, separation, chromatography and electronics
[9–11, 14–18]. More recently, a family of PMOs called
bifunctional periodic mesoporous organosilicas (BPMOs)
involving functional moieties both in wall and mesopores
have created and received exciting attention in green
chemistry processes [19–21]. BPMO materials have a
lot of applications in heterogonous catalysis, biosensors,
enantiomeric separation, light harvesting, drug release and
so on [22–32]. To date several BPMOs have been prepared
by immobilization of metal and Schiff-base complexes on
PMOs for different chemical applications [33–37]. Some
of recently developed BPMOs including catalytic centers
are Pd-LHMS-3 [25, 38], Ti-LHMS-3 [39], V-LHMS-1
[40], Au/PME-ED [41], Au-HS/SO3H-PMO(Et) [42] and
Pd-PPh2-PMO(Ph) [43] that have been used as catalyst in
different organic reactions [8, 19, 21, 44–47]. However, to
now there is any report on the preparation of BPMO with
isatin moieties in the literature [48–55]. Accordingly, in
the present study a novel BPMO nanomaterial containing
isatin-Schiff base functional groups has been prepared and
applied as efficient support for immobilization of manga-
nese catalyst.
According to aforementioned notes and in continuous
of our recent studies in the design, preparation and appli-
cations of new supported catalytic systems [52, 64–69],
herein a novel bifunctional periodic mesoporous organo-
silica supported isatin-Schiff-base/manganese (BPMO@
ISB/Mn(II)) catalyst is prepared and characterized using
several techniques. The BPMO@ISB/Mn(II) nanocata-
lyst was successfully applied in the one-pot synthesis of
dihydropyrano[3,2-c]chromene derivatives in aqueous media
at room temperature.
2 Experimental Section
2.1 General
All chemicals and reagents such as tetramethoxysilane
(TMOS), bis(triethoxysilyl)benzene (BTEB), 3-aminopro-
pyltrimethoxysilane (APTS), isatin, pluronic P123, KCl,
HCl, malononitrile, 4-hydroxycoumarin and all applied
aldehydes were purchased from Merck and Fluka compa-
nies. The reaction progress was monitored using TLC. The
morphology of the material was investigated using SEM,
Philips, XL30 emission electron microscope. TGA was car-
ried out on NETZSCH STA 409 PC/PG apparatus. Low
angle powder X-ray diffraction pattern was recorded by a
Panalytical model X’ Pert Pro focus diffractometer with Cu
Kα radiation operated at 40 kV and 40 mA. TEM analysis of
the catalyst was obtained using FEI TECNAI 12 BioTWIN
transmission electron microscope. IR spectra were recorded
on a Brucker-Vector 22 spectrometer. Melting points were
determined using a KSB1N, Kruss apparatus in open capil-
lary tubes.
On the other hand, dihydropyrano[3,2-c]chromenes
are among important and attractive pharmaceutical com-
pounds that exhibit a wide range of biological activities
such as myorelaxant, diuretic, analgesic, anticoagulant,
anti-tumor, anticancer, cytotoxicityand and anti-HIV
[56–60]. In addition, these can be used as antimicrobial,
anti-tuberculosis agents and cognitive enhancers for the
treatment of Alzheimer’s disease, neurodegenerative dis-
eases, amyotrophic lateral sclerosis, Parkinson’s disease,
2.2 Preparation of BPMO@ISB
Firstly, phenylene based periodic mesoporous organosilica
(Ph-PMO) was prepared via hydrolysis and co-condensation
of bis(triethoxysilyl)benzene (BTEB) and tetramethoxysi-
lane (TMOS) in the presence of pluronic P123 surfactant
under acidic conditions (Scheme 1) [51, 65, 70]. It is impor-
tant to note that the molar ration between these precursors
was (TMOS/BTEB, 70:30). Then, Ph-PMO supported
1 3

Phenylene and Isatin Based Bifunctional Mesoporous Organosilica Supported…
Scheme 1 Preparation of the BPMO@ISB/Mn(II) nanocatalyst
propylamine (Ph-PMO-Pr-NH2) was prepared through
chemical grafting of 3-aminopropyl-trimethoxysilane
(APTS) onto Ph-PMO [51]. Typically, 1 g of Ph-PMO was
added in dry toluene (30 mL) and stirred at room tempera-
ture. After complete dispersion of Ph-PMO, APTS (4 mmol)
was added into reaction vessel and resulted mixture was
refluxed for 24 h under argon atmosphere. After cooling to
room temperature, the obtained solid was collected through
filtration, washed several times with ethanol and then dried
at 65 °C for 10 h to yield Ph-PMO-Pr-NH2. After that, the
Ph-PMO supported isatin-Schiff-base (BPMO@ISB) was
prepared [35, 37] as following: Ph-PMO-Pr-NH2 (1 g) was
well dispersed in toluene (20 mL) and isatin (8 mmol) was
added. The resulting mixture was refluxed for 24 h under
argon atmosphere. Finally, the obtained mixture was cooled
to room temperature, filtered, washed completely with etha-
nol and dried at 70 °C for 12 h to give a solid material called
BPMO@ISB.
means of the Mn-content obtained from inductively coupled
plasma/optical emission spectroscopy (ICP-OES).
2.4 Synthesis of Dihydropyrano[3,2‑c]chromene
Derivatives in the Presence of BPMO@ISB/Mn(II)
Nanocatalyst
A mixture of aldehyde (1 mmol), 4-hydroxycoumarin
(1 mmol), malononitrile (1.2 mmol), and BPMO@ISB/
Mn(II) (20 mg) were added in aqueous ethanol (H2O/EtOH,
1:1, 5 mL). This was magnetically stirred at room tempera-
ture for appropriate time indicated in Table 3. After comple-
tion of the reaction, monitored by TLC, the resulted mix-
ture was dissolved in warm ethanol (10 mL) and the catalyst
was separated by filtration. Then, the pure products were
obtained after recrystallization in ethanol.
2.5 Procedure for the Recovery of BPMO@ISB/Mn(II)
2.3 Preparation of BPMO@ISB/Mn(II) nanocatalyst
To study the recoverability of the BPMO@ISB/Mn(II)
nanocatalyst, benzaldehyde (1 mmol), 4-hydroxycoumarin
(1 mmol), malononitrile (1.2 mmol) and BPMO@ISB/
Mn(II) (20 mg) were added in aqueous ethanol (H2O/EtOH,
1:1) while stirring at room temperature. After completion
of the reaction, the catalyst was separated by simple fil-
tration, washed and dried at 70 °C for 2 h. The recovered
catalyst was then reused in the next run charged with the
same amounts of starting materials under above mentioned
conditions. These steps were repeated and it was found that
the catalyst could be recovered and reused at least 5 times
without significant decrease in efficiency.
For the preparation of BPMO@ISB/Mn(II), the BPMO@
ISB (1 g) was added in DMSO (20 mL) and stirred at room
temperature. After complete dispersion of this nanomaterial,
a prepared DMSO solution of Mn(NO3)2∙4H2O (4 mmol)
was added in the reaction vessel and it was stirred for 24 h
at room temperature under argon atmosphere. The resulted
mixture was then filtered and washed with absolute ethanol
to remove unreacted manganese nitrate. The obtained solid
was dried at 70 °C for 10 h to deliver a uniform powder
called BPMO@ISB/Mn(II) nanocatalyst. The loading of
the manganese was obtained to be 0.22 mmol Mn/g by the
1 3

M. Norouzi, D. Elhamifar
2.6 Procedure for the Filtration Test
Filtration test was performed to show whether active man-
ganese catalyst is leached from the solid material during
the reaction or not. For this purpose, the experiment was
performed in a water/ethanol solution containing benzalde-
hyde (1 mmol), 4-hydroxycoumarin (1 mmol), malononitrile
(1.2 mmol) and BPMO@ISB/Mn(II) (20 mg) at room tem-
perature. After about 50% of the reaction was completed,
the BPMO@ISB/Mn(II) nanocatalyst was separated using
simple filtration and then the residue was allowed to pro-
gress at room temperature for 2 h.
3 Results and Discussion
For the preparation of BPMO@ISB/Mn(II) nanocatalyst,
firstly phenylene-based periodic mesoporous organosilica
(Ph-PMO) was synthesized via surfactant directed simulta-
neous hydrolysis and co-condensation of bis(triethoxysilyl)
benzene and tetramethoxysilane under acidic conditions.
This was then modified with 3-aminopropyltrimethoxysi-
lane to afford Ph-PMO-Pr-NH2. The bifunctional PMO sup-
ported isatin-Schiff-base (BPMO@ISB) was then prepared
by treatment of Ph-PMO-Pr-NH2 with isatin in toluene
under reflux conditions. After that, the BPMO@ISB was
applied as effective support for successful immobilization
of manganese to deliver BPMO@ISB/Mn(II) nanocatalyst
(Scheme 1). As shown in Scheme 1, during the first steps
the supported amine moieties reacted with carbonyl groups
of isatin to form Schiff-base ligands that are appropriate for
immobilization of metallic sites. In the next step, the man-
ganese salt (Mn(NO3)2∙4H2O) was reacted with supported
isatin moieties to prepare isatin-Schiff-base/Mn complex.
The physiochemical properties of the BPMO@ISB/
Mn(II) nanocatalyst were studied using FT-IR, SEM, TEM,
TGA and EDX techniques. Firstly, the FT-IR analysis of
the Ph-PMO, Ph-PMO-P123 and BPMO@ISB/Mn(II) was
performed to study the functionality of the materials in the
range of 400–4000 cm−1 (Fig. 1). For all materials, the
characteristic bands of aromatic C=C, aliphatic C–H, aro-
matic C–H and H–O stretching vibrations were appeared,
respectively, at 1556, 2944, 3095 and 3400 cm−1. Moreo-
ver, for these samples the asymmetric and symmetric
stretching vibrations of Si–O–Si bonds were observed at
956 and 1070 cm−1. For Ph-PMO-P123 the bands observed
at 2920 and 2850 were due to the aliphatic C–H stretching
vibrations of P123 surfactant (Fig. 1a). Interestingly, for
Ph-PMO (Fig. 1b) and BPMO@ISB/Mn(II) (Fig. 1c), the
latter peaks were eliminated indicating successful removal
of surfactant during extraction process. It is also impor-
tant to note that for BPMO@ISB/Mn(II) sample the peak
Fig. 1 FTIR spectra of a Ph-PMO-P123, b Ph-PMO and c BPMO@
ISB/Mn(II) nanomaterials
Fig. 2 Thermal gravimetric analysis (TGA based on mg, a), (based
on percent, b), derivative TG (DTG, c) and differential thermal analy-
sis (DTA, d) curves of the BPMO@ISB/Mn(II) nanocatalyst
cleared at 1621 is assigned to C=N bond confirming suc-
cessful formation of Schiff-base (SB) complex onto mate-
rial surface (Fig. 1c).
Thermal stability of the BPMO@ISB/Mn(II) nanocatalyst
was evaluated using thermal gravimetric analysis (TGA).
As seen in Fig. 2, the BPMO@ISB/Mn(II) undergoes the
first weight loss below 100 °C which is due to removal
of adsorbed or trapped water and alcoholic solvents. The
main weight loss appearing between 270 and 800 °C is
corresponded to the decomposition of organic groups (pro-
pylamine and isatin) grafted onto PMO surface and also phe-
nylene moieties incorporated in the body of BPMO@ISB/
Mn(II). These results indicate high thermal stability of the
designed nanocatalyst.
1 3

Phenylene and Isatin Based Bifunctional Mesoporous Organosilica Supported…
Fig. 5 SEM image of BPMO@ISB/Mn(II) nanocatalyst
Fig. 3 EDX spectrum of the BPMO@ISB/Mn(II) nanocatalyst
Fig. 6 Low-angle X-ray diffraction analysis of a BPMO@SB and b
BPMO@SB/Mn(II) nanomaterials
Fig. 4 TEM image of the BPMO@ISB/Mn(II) nanocatalyst
nanocatalyst showed a peak at 2θ = 1.1° indicating a
mesoporous structure for these materials (Fig. 6). The lower
intensity of aforementioned peak for the BPMO@SB/Mn(II)
catalyst confirms successful immobilization of manganese
moieties onto BPMO@SB surface.
The EDX spectrum of BPMO@ISB/Mn(II) nanocatalyst
(Fig. 3) showed the signals of carbon, nitrogen, oxygen, sili-
con and manganese. This result is in good agreement with
the results of TG and FTIR analyses confirming successful
incorporation and/or immobilization of phenylene, propyl-
isatin and manganese moieties onto/into material framework.
The TEM image of BPMO@ISB/Mn(II) nanocatalyst
demonstrated a structure with well-ordered channels that
proves the presence of two dimensional mesostructure with
high regularity for the material (Fig. 4). The SEM image
also clearly showed the presence of high-ordered spherical
particles for the BPMO@ISB/Mn(II) catalyst (Fig. 5). These
results successfully confirm high ability and efficiency of the
designed catalyst in the catalytic process.
The BET experiment of the BPMO@ISB, BPMO@ISB/
Mn(II) and recovered BPMO@ISB/Mn(II) [RBPMO@ISB/
Mn(II)] materials were also performed and according to this
analysis, the BET surface area for BPMO@ISB, BPMO@
ISB/Mn(II) and RBPMO@ISB/Mn(II) was 647 m2/g,
553 m2/g and 462 m2/g, respectively (Table 1). Moreo-
ver, total pore volume was calculated to be 1.27, 1.20 and
1.02 cm3/g for the BPMO@ISB, BPMO@ISB/Mn(II) and
RBPMO@ISB/Mn(II) materials (Table 1). The decrease in
the surface area and pore diameter of modified BPMO@ISB
is corresponded to the immobilization of APTS, isatin and
Mn(II) complex onto the mesoporous pores. These results
are in good agreement with TEM and PXRD analyses and
The low angle powder X-ray diffraction (LAPXRD)
analysis of both BPMO@SB and BPMO@SB/Mn(II)
1 3

M. Norouzi, D. Elhamifar
Table 1 Structural parameters of BPMO@ISB, BPMO@ISB/Mn(II)
reaction conditions were optimized to determine a suitable
catalyst loading and solvent (Table 2). At first, the reac-
tion was performed without catalyst at room temperature
(Table 2, entry 1) that no considerable product was obtained.
Where 10 mg of catalyst was used, about 53% yield was
resulted (Table 2, entry 2). The best conversion was obtained
in the presence of 20 mg of catalyst indicating the key role of
catalyst loading in the reaction progress (Table 2, entry 3).
In the next, the effect of solvent in the reaction progress was
studied (Table 2, entries 4–10). Among different solvents,
the best result was obtained in aqueous ethanol (H2O/EtOH,
1:1, Table 2, entry 9).Also, the effect of volume of solvent
showed that the use of 5 mL gives the best conversion
(Table 2, entries 8–10). Accordingly the use of 20 mg of cat-
alyst at room temperature in aqueous ethanol were selected
as optimum conditions. To study the individual impact of
manganese species during this catalytic process, the effi-
ciency of the BPMO@ISB/Mn(II) was compared with those
of Ph-PMO-Pr-NH2 and BPMO@ISB nanomaterials. The
results showed that in the presence of both Ph-PMO-Pr-NH2
and BPMO@ISB materials, the reaction is not performed
and RBPMO@ISB/Mn(II) determined from BET experiments
Sample
BET surface
Pore diam- Pore
area (m2 g−1
)
eter (nm)
volume
(cm3 g−1
)
BPMO@ISB
BPMO@ISB/Mn(II)
RBPMO@ISB/Mn(II)
647
553
462
5.1
4.5
3.9
1.27
1.20
1.02
successfully confirm the presence of a well-ordered meso-
structure for the materials. It is also important to note that
the decrease in the surface area, pore volume and pore diam-
eter for the recovered catalyst in comparison with its parent
is attributed to partial saturation of mesochannels with start-
ing materials and reaction products.
After characterization, the catalytic activity of the
BPMO@ISB/Mn(II) was investigated in the synthesis of
dihydropyrano[3,2-c]chromene derivatives. For this, the
condensation of benzaldehyde with malononitrile and
4-hydroxycoumarin was selected as a model reaction. The
Table 2 The effect of catalyst loading and solvent in the preparation of dihydropyrano[3,2-c]chromenes
Entry
Catalyst
Catalyst (mg)
Time (min)
Solvent
Yield (%)a
1
2
3
4
5
6
7
8
–
–
120
15
15
15
15
15
15
15
15
15
15
15
–
–
–
–
–
BPMO@ISB/Mn(II)
BPMO@ISB/Mn(II)
BPMO@ISB/Mn(II)
BPMO@ISB/Mn(II)
BPMO@ISB/Mn(II)
BPMO@ISB/Mn(II)
BPMO@ISB/Mn(II)
BPMO@ISB/Mn(II)
BPMO@ISB/Mn(II)
Ph-PMO-Pr-NH2
BPMO@ISB
10
15
20
20
20
20
20
20
20
20
20
37
54
76
80
50
88
90
95
95
<5
<5
EtOH (5 mL)
CH3CN (5 mL)
H2O (5 mL)
H2O/EtOH (3 mL)
H2O/EtOH (5 mL)
H2O/EtOH (7 mL)
H2O/EtOH (5 mL)
H2O/EtOH (5 mL)
9
10
11
12
aConditions: benzaldehyde (1 mmol), malononitrile (1.2 mmol) and 4-hydroxycoumarin (1 mmol) at room temperature
aIsolated yield
1 3

Phenylene and Isatin Based Bifunctional Mesoporous Organosilica Supported…
and only a low yield of product is obtained (Table 2, entry
9 vs. entries 11 and 12). This confirms that the reaction is
mainly catalyzed by supported manganese species.
[51]. Then, Micheal addition of cyanocinnamonitrile with
4-hydroxy coumarin, followed by cyclization and rear-
rangement provides desired product [71, 72]. In order to
extend the scope of the present method and to evaluate the
efficiency of the BPMO@ISB/Mn(II) catalyst for organic
reactions, the replacement of 4-hydroxy-co-mamarin with
dimedone under the same conditions as above provided cor-
responding tetrahydrobenzo [b] pyran derivatives in high
yields and short reaction times (Table 3, entries 10 and 11).
Since recovery and reusability of catalyst in industrial
and commercial applications as well as in green chemistry
are very important, in the next the recoverability and reus-
ability of the BPMO@ISB/Mn(II) nanocatalyst were studied
in the synthesis of dihydropyrano [3,2-c] chromenes. In this
In optimized conditions, the scope and generality of this
process were further studied with a set of different aldehydes
containing either electron-withdrawing (4-nitobenzaldehyde,
4-cyanobenzaldehyde, 2-furfural and 4-fluorobenzaldehyde)
and electron-donating (such as 4-methylbenzaldehyde) sub-
stituents. As shown, both of these substrates delivered cor-
responding coupling products in high to excellent yields
without formation any side product in very short reaction
time (Table 3). It is important to note that this reaction is
initiated by manganese complex assisted Knoevenagel
condensation to provide cyanocinnamonitrile intermediate
Table 3 Preparation of dihydropyrano[3,2-c]chromenes and tetrahydrobenzo[b]pyran derivatives in the presence of BPMO@ISB/Mn(II) nano-
catalyst
Entry
Ar
R
Time (min)
Yield (%)a
TONb
Mp (°C)
M.P (°C)Ref
1
2
3
4
5
6
7
8
C6H5
CN
CN
CN
CN
CN
CN
CN
CN
15
25
10
10
10
8
15
15
18
10
15
95
88
93
92
92
95
90
90
92
95
92
216
200
211
209
209
216
205
204
209
216
209
255–257
259–261
223–226
260–262
259–262
255–256
254–256
251–254
242–244
228–230
217–220
256–258 [73]
258–260 [74]
224–226 [75]
262–263 [73]
262–264 [76]
256–258 [73]
254–256 [74]
253–255 [77]
241–243 [73]
226–228 [78]
216–218 [79]
4-MeC6H5
4-CNC6H5
4-FC6H5
3-NO2C6H5
4-NO2C6H5
4-BrC6H5
2-furfural
4-NO2C6H5
4-CNC6H5
4-MeC6H5
9
COOEt
CN
CN
10c
11c
Conditions: aldehyde (1 mmol), malononitrile (1.2 mmol), 4-hydroxycoumarin (1 mmol) and BPMO@ISB/Mn(II) catalyst (20 mg, 0.44 mol%)
in aqueous ethanol (1:1, H2O/EtOH) at room temperature
aIsolated yields
bTON turnover number (defined as mmol of product/mmol of catalyst)
cAldehyde (1 mmol), malononitrile (1.2 mmol), dimedone (1 mmol) and BPMO@ISB/Mn(II) catalyst (20 mg) in aqueous ethanol (1:1, H2O/
EtOH) at room temperature
1 3

M. Norouzi, D. Elhamifar
part of our study, it was found that the BPMO@ISB/Mn(II)
nanocatalyst could be recycled at least five times without
considerable loss in its activity (Fig. 7).
a
The FT-IR spectrum of the recovered BPMO@ISB/
Mn(II) nanocatalyst (Fig. 8a) was also performed to inves-
tigate the stability of Schiff-base moieties during reaction
process and the result was compared with the fresh BPMO@
ISB/Mn(II) nanocatalyst (Fig. 8b). Interestingly, both of
these spectra showed the presence of a band at 1621 cor-
responding to C=N bond of Schiff-base group indicating
the stability of this ligand under applied reaction conditions.
In the next, the SEM analysis of the recovered BPMO@
ISB/Mn(II) nanocatalyst was performed and the result was
compared with the SEM image of the fresh catalyst. As
shown, the morphology of the recovered catalyst is approxi-
mately the same as fresh catalyst indicating high stability of
the material structure during catalytic process (Figs. 5 vs. 9).
To investigate the efficacy of the BPMO@ISB/Mn(II)
catalyst in the synthesis of dihydropyrano [3,2-c]chromenes,
we compared the results obtained in this work with those
reported in the literature mediated by other catalysts
(Table 4). The results showed that the new catalyst is equally
or more efficient catalyst than previously reported systems.
The advantages of the present work in comparison to previ-
ously reported ones are high surface area, high uniformity
and stability of the support, high lipophilicity of the mes-
ochannals simplifying well-diffusion of organic substrates
and mild reaction conditions that make this method from
the green chemistry point of view more environmentally
friendly.
b
3900
3400
2900
2400
1900
]
1400
900
400
Wavenumber[cm-1
Fig. 8 FTIR spectrum of a recovered BPMO@ISB/Mn(II) and b
fresh BPMO@ISB/Mn(II) nanocatalyst
simple filtration and then reaction mixture was allowed to
continue under applied conditions. Interestingly, after 2 h
only a trace conversion of starting materials was found.
The latter studies successfully confirm high recoverabil-
ity, reusability, reactivity, stability and durability of desired
catalyst under applied conditions.
4 Conclusion
In summary, for the first time a novel manganese containing
phenylene and isatin-Schiff-base based bifunctional PMO
[BPMO@ISB/Mn(II)] was prepared and characterized. The
FT-IR, TG and EDX analyses successfully confirmed well-
incorporation and immobilization of organic and inorganic
moieties into/onto material framework. The TEM image
demonstrated the presence of high-ordered two-dimensional
mesostructure for this catalyst. The SEM image also showed
Although no significant decrease in the efficiency of
the catalyst was observed after the reusability test, to show
whether any BPMO@ISB/Mn(II) complex is leached from
the BPMO@ISB surface during the reaction progress, a
filtration test was performed in the model reaction after
~ 50% of the coupling reaction was completed. For this,
the BPMO@ISB/Mn(II) nanocatalyst was separated using
100
90
80
70
60
50
40
30
20
10
0
1
2
3
4
5
6
Yield (%)
95
92
90
90
88
85
Time (min)
15
17
18
20
23
25
Fig. 7 Reusability of the BPMO@ISB/Mn(II) nanocatalyst in the
synthesis of dihydropyrano [3,2-c]chromenes
Fig. 9 SEM image of the recovered BPMO@ISB/Mn(II) nanocatalyst
1 3

Phenylene and Isatin Based Bifunctional Mesoporous Organosilica Supported…
Table 4 Comparison of
Entry
Catalyst
Conditions
References
activity of BPMO@ISB/Mn(II)
catalyst with the previously
reported catalytic systems in
the synthesis of dihydropyrano
[3,2-c]chromenes
1
2
3
4
5
6
7
8
Fe3O4@SiO2-imid-PMA
SBPPSPa
H2O, reflux or ultrasonic
H2O/EtOH, reflux
H2O/EtOH, 70 °C
MeOH, reflux
Solvent free, 80 °C
H2O, reflux
[80]
[81]
[82]
[83]
[84]
[85]
[86]
This work
CTMAB-bentoniteb
c
RuBr2(L)4
SiO2/H3PW12O40
γ-Fe2O3@HAp-Si-(CH2)3-AMPd
Polypyrrole/Fe3O4/CNTe
BPMO@ISB/Mn(II)
Solvent free, 90 °C
H2O/EtOH, r.t
aSilica-bonded N-propylpiperazine sodium n-propionate
bSurfactant modified bentonite
cRu(II) complexes bearing tertiary phosphine ligands
dMagnetic hydroxyapatite encapsulated γ-Fe2O3 supported (2-aminomethyl) phenol
eCarbon nanotube (CNT)
14. Hatton B, Landskron K, Whitnall W, Perovic D, Ozin GA
(2005) Acc Chem Res 38:305–312
the presence of particles with spherical morphology for this
material. The BPMO@ISB/Mn(II) was successfully applied
as an effective and recoverable catalyst for the synthesis of
dihydropyrano [3,2-c]chromene derivatives and gave prod-
ucts in high to excellent yields at room temperature and short
times. This catalyst was easily recovered and reused several
times with keeping its performance in aqueous ethanol as
green solvent. The high efficiency of the present catalytic
system is attributed to good mesoporosity of the designed
catalyst, high stability and durability of active sites, the use
of green solvent and performing reaction at very short times
at room temperature.
15. Hunks WJ, Ozin GA (2005) J Mater Chem 15:3716–3724
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Acknowledgements The authors thank the Yasouj University and the
Iran National Science Foundation (INSF) for supporting this work.
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Affiliations
Meysam Norouzi1 · Dawood Elhamifar1
1
* Dawood Elhamifar
Department of Chemistry, Yasouj University,
d.elhamifar@yu.ac.ir
75918-74831 Yasouj, Iran
1 3