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Microporous and Mesoporous Materials 227 (2016) 23e30

Contents lists available at ScienceDirect

Microporous and Mesoporous Materials


journal homepage: www.elsevier.com/locate/micromeso

Iron (III)-doped, ionic liquid matrix-immobilized, mesoporous silica


nanoparticles: Application as recyclable catalyst for synthesis of
pyrimidines in water
Hossein Naeimi a, *, Vajihe Nejadshaee a, Mohammad Reza Islami b
a
b

Department of Organic Chemistry, Faculty of Chemistry, University of Kashan, Kashan 87317, Islamic Republic of Iran
Chemistry Department, Shahid Bahonar University of Kerman, Kerman 76169, Islamic Republic of Iran

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 5 December 2015
Received in revised form
13 February 2016
Accepted 17 February 2016
Available online 21 February 2016

A novel ionic liquid functionalized iron-containing mesoporous silica nanoparticles (Fe-MCM-41-IL) was
prepared by anchoring a triazolium ionic liquid on the surface of Fe loaded MCM. The result samples
were characterized by XRD, FT-IR, EDS, XRF, HRTEM, FE-SEM, VSM, N2 adsorptionedesorption analysis
and AAS techniques. The use of Fe-MCM-41-IL as an efcient reusable heterogeneous catalyst allows onepot synthesis of pyrimidine derivatives under mild condition in high yields from substituted aldehydes,
two moles of 2-thiobarbituric acid and ammonium acetate. Operational simplicity, low cost, high yields,
eco-friendly reaction conditions, economical catalyst, reusability and easy recovery of the catalyst make
this procedure greener than the other reported works.
2016 Elsevier Inc. All rights reserved.

Keywords:
Mesoporous
Nanoparticles
Synthesis
Ionic liquid
Pyrimidines
Catalyst

1. Introduction
Within the past decade, mesoporous silica materials (MCM-41)
have increased in popularity for heterogenous catalyst purposes, in
part because their large pore volume, high surface area, uniform
pore size distribution, regular structure and high thermal stability
[1e4]. Generally, the pure silica MCM has limited catalytic activity
but active catalytic sites can be generated in MCM by isomorphously substituting silicon with a metal [5]. Several studies
have been dedicated to the investigation of transition-metalsubstituted MCM-41 because of their wide range of applications
in catalysis [6,7]. Specically, the substitution of iron species in the
framework of MCM such as Fe-MCM-41 has a higher specic activity in the organic reactions [8e16]. In recent decades ionic liquids phases have attracted signicant attention in the scientic
community as an alternative reaction medium for homogeneous
catalysis [17,18]. Although the ability of liquideliquid biphase
catalysis in ionic liquid has successfully been demonstrated but
heterogeneous catalysts are still preferred by industry because the

* Corresponding author.
E-mail address: naeimi@kashanu.ac.ir (H. Naeimi).
http://dx.doi.org/10.1016/j.micromeso.2016.02.036
1387-1811/ 2016 Elsevier Inc. All rights reserved.

ease of separation. Recently, the ionic liquids supported on the solid


such as amorphous silica and mesoporous silica hybrid [19e24],
magnetic nanoparticle [25], especially acidic types have attracted
increasing interest in organic synthesis, because they can provide
green and efcient media for organic reactions. The development of
efcient methods for constructing substituted six-membered nitrogen-containing heterocycles such as; 1,4-dihydropyridines (1,4DHPs) has been the subject of extensive research due to the vast
number of natural products, pharmaceutical and agrochemical
agents, and functional materials containing these ring systems
[26e29].
The traditional procedures for the synthesis of 1,4-DHPs rely on
condensation of amine and carbonyl compounds. Much effort has
been dedicated to the development of new methodologies to access
1,4-DHPs [30]. Among a number of methodologies developed to
date, the [2211] Hantzsch reaction using two 1,3-dicarbonyl
compounds, an amine and an aldehyde is a conventional and succinct approach to synthesize symmetrical 1,4-DHPs [31,32]. Various
methods for the preparation of 1,4-DHPs and pyrimidine-fused
heterocycles by using cyclic diketone, aromatic aldehydes and
amines or ammonium acetate under different conditions have been
reported [26,33,34]. Initially, herein, we present the preparation
and characterization of supported novel ionic liquid catalyst based

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H. Naeimi et al. / Microporous and Mesoporous Materials 227 (2016) 23e30

on functionalized iron-containing mesoporous silica nanoparticles


(Fe-MCM-41-IL). Then, we focus our attention on a simple, green
and efcient method for the synthesis of biological active pyrimidine derivatives from a wide variety of aldehydes, 2-thiobarbituric
acid and ammonium acetate in high yields and short reaction times.
2. Results and discussion
2.1. Catalyst preparation
Novel ionic liquid functionalized iron-containing MCM-41,
named Fe-MCM-41-IL as a nanocatalyst was prepared based on the
following procedure. Initially, the Fe-MCM-41 was prepared by the
direct-hydrothermal technique of ferric chloride (FeCl3$6H2O),
TEOS as source silica and cetyl trimethyl ammonium bromide
(CTAB) as a structural directing surfactant in an alkaline solution
according to the literature procedure [35]. Then, the triazole
ammonium based ionic liquid including 1,2,3-triazole functionality
on one side and a triethoxysilyl moiety on the other side was
synthesized and subsequently grafted to the surface of Fe-MCM-41
in reuxing toluene for 24 h (Scheme 1).
2.2. Catalyst characterization
Fig. 1. FT-IR spectra of a) MCM-41, b) Fe-MCM-41 and c) Fe-MCM-41-IL.

Fourier transform-infrared (FT-IR) spectra of MCM-41, Fe-MCM41 and Fe-MCM-41-IL are shown in Fig. 1. For all samples the bands
characteristic of the MCM-41 framework can be clearly seen. The
slight shift of the 1109 cm1 band of SieOeSi into the 1081 cm1
band of SieOeFe vibrations allowed the conclusion that the heteroatoms were incorporated into the framework of MCM-41 and

H3CO

OCH3
Si
OCH3

i)
Cl
N
Ph

the formation of FeeOeSi bonds [36]. In Fig. 1c, the absorption


peaks at 2924 and 2855 cm1 were assigned to aromatic CeH and
aliphatic CeH of the IL structure, respectively. The presence of these
peaks conrms successful immobilization of IL on the surface of

C2H5
N

Ph

OH

OCH3
Si OCH3
H3CO

HO3S

O
(IL)

CTAB

iii) H2SO4

C2H5

Ph

NaOH

O
S O
O

C2H5
HSO4-

FeCl3.6H2O

ii)

OCH3
Si OCH3
H3CO

1) Washed

stirred

550 oC, 6h

TEOS
2 h, rt

2) Dried at 100 oC

H2O

Fe-MCM-41
IL

HSO4HO3S

N
N
Ph

C2H5
O

Toluene,
24 h

Si O
H3CO O

Fe-MCM-41-IL
Scheme 1. Different Steps for Synthesis of Fe-MCM-41-IL.

H. Naeimi et al. / Microporous and Mesoporous Materials 227 (2016) 23e30

Fig. 2. XRD pattern of Fe-MCM-41.

Fe-MCM. The additional peak was observed at 1520 cm1 related to


C]N bond. Furthermore, the bands at 3438 and 3425 cm1 suggest
that there are OH groups on the mesoporous Fe-MCM-41 and after
the immobilization of IL on the Fe-MCM-41 surface (Fig. 1a and b).
The low-angle X-ray diffraction (XRD) pattern of Fe-MCM-41 is
depicted in Fig. 2. Fe-MCM-41pattern showed a distinct broad peak
which account for the Bragg plane (100) intense reection, indicating the regular arrangement of mesoporous with hexagonal
symmetry [12,37].
The structure of the prepared materials was further veried
using eld emission-scanning electron microscopy (FE-SEM) and

25

high-resolution transmission electron microscopy (HRTEM) images. As can be clearly seen, Fe-MCM-41 have a well-dened
spherical structure with relatively narrow size distribution and its
FE-SEM image indicated that the diameter of the spherical particles
in the about 85e87 nm (Fig. 3a). After functionalization with IL, the
Fe-MCM-41-IL kept their spherical structure with particle size of
about 95e98 nm as shown in the FE-SEM images (Fig. 3b). The
results indicated that the FE-SEM images of Fe-MCM-41 and FeMCM-41-IL exhibited similar structure with increase of particles
size which provided strong evidence that the mesoporous structure
of the supporting retained after the grafting process.
Fig. 3c and d are shown the HRTEM images of Fe-MCM-41 and
Fe-MCM-41-IL samples. As can be seen from these images, the wellordered pore arrangements and the iron uniform introduction into
mesoporous silicate framework were visible. Also, the long-rang
order and mesoporous structure arrays were not disturbed significantly after Fe doping.
The Fe and Si contents in Fe-MCM-41 were determined using Xray uorescence analysis (XRF) and their results were shown that
the molar ratio of Fe/Si was 13.47. Furthermore, the closeness of
ionic liquid groups on the Fe-MCM-41-IL surface was further
conrmed by energy dispersive spectrometer (EDS) (Fig. 4). The
obtained results by EDS were as follows (%): C, 5.40; N, 5.25; Si,
17.38; O, 61.32; S, 6.92; Fe, 3.72.
N2
adsorptionedesorption
isotherms
and
the
BarretteJoynereHalenda (BJH) pore-size distribution curves of FeMCM and Fe-MCM-41-IL are depicted in Fig. 5. The samples displayed type II isotherms [38] and capillary condensation at relative
pressures of 0.3 < P/P0 < 0.5, which was the characteristic of
mesoporous materials. The textural properties of Fe-MCM-41 were
substantially maintained after immobilization of triazolium ionic
liquid.

Fig. 3. FE-SEM images of a) Fe-MCM-41, b) Fe-MCM-41-IL and TEM images of c) Fe-MCM-41, d) Fe-MCM-41-IL.

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H. Naeimi et al. / Microporous and Mesoporous Materials 227 (2016) 23e30

Fig. 6. Magnetization curves for the prepared Fe-MCM-41 and Fe-MCM-41-IL.

Fig. 4. EDS pattern of Fe-MCM-41-IL.

can be related to incorporation of high Fe content into the framework of MCM-41.


The magnetic properties of the Fe-MCM-41 and Fe-MCM-41-IL
catalyst were investigated using a vibrating sample magnetometer at room temperature. As illustrated in Fig. 6, the magnetization
curves of the prepared materials exhibit no hysteresis loop which
demonstrates its super paramagnetic characteristics. Moreover, the
good magnetic properties of the prepared catalyst were revealed by
complete and easy attraction using an external magnet. The saturation magnetization of the Fe-MCM-41 and Fe-MCM-41-IL were
found to be 2.80 emu g1 and 1.74 emu g1, respectively as
measured using vibrating sample magnetometer (VSM). Since,
ionic liquid was coated with Fe-MCM-41 mesoporous hybrid a
decrease in saturation magnetization can be observed after coating.
Furthermore, the total surface acidity for the Fe-MCM-41 and
Fe-MCM-41-IL were determined by sodium hydroxide titration. In
this measurement procedure, the pH of Fe-MCM-41 and Fe-MCM41-IL catalyst were 5.87 and 1.04 that can be equal to loading the
3.37  105 and 2.19 mmol (H) g1, respectively.
2.3. Investigation of catalyst activity in synthesis of pyrimidines

Fig. 5. N2 adsorptionedesorption isotherms Fe-MCM-41 and Fe-MCM-41-IL.

The surface area, pore volume, and pore diameters of Fe-MCM


and Fe-MCM-41-IL are listed in Table 1. The surface area
decreased from 307 to 225 m2 g1 with supported IL on the FeMCM-41. Also, there is a negligible change in pore volume from
0.42 to 0.38 cm3 g1 after grafting process. It could be concluded
that introduction of ionic liquid signicantly affected the surface
area and pore volume of the support. Moreover, the smaller surface
area of Fe-MCM-41 compared with previous Fe-MCM-41 samples

For the purpose of the catalytic activity comparison of Fe-MCM41 and Fe-MCM-41-IL, the treatment of 2-thiobarbituric acid,
benzaldehyde and ammonium acetate affording pyrimidine were
examined in the amount of different catalysts. The results of the
optimized conditions are summarized in Table 2. These observations clearly emphasized the existence of a signicant effect between grafted ionic liquid groups and without ionic liquid on the
Fe-MCM-41 surface. Therefore, the Fe-MCM-41-IL catalyst
showed excellent catalytic performance rather than Fe-MCM-41
that accordance to strong acidic properties of Fe-MCM-41-IL catalyst was justied.

Table 1
Surface Properties of Fe-MCM-41 and Ionic-liquid modied Fe-MCM-41 (Fe-MCM-41-IL).
Sample

Surface areaa (m2 g1)

Pore sizeb (nm)

Pore volumec (cm3 g1)

Fe-MCM-41
Fe-MCM-41-IL

307.98
225

8.42
8.25

0.42
0.38

a
b
c

Calculated by the BET model.


Calculated by the BJH model from the desorption isotherm.
Total pore volume at P/P0 0.99.

H. Naeimi et al. / Microporous and Mesoporous Materials 227 (2016) 23e30


Table 2
Effect of catalyst amount on the reaction.a

Fe-MCM-41-IL

Fe-MCM-41

Entry

Amount of catalyst
(mg)

Yield (%)

Amount of catalyst
(mg)

Yield (%)

1
2
3
4

10
15
20
25

80
84
89
89

10
15
20
25

trace
trace
trace
trace

a
Reaction condition: aldehyde (1 mmol), 2-Thiobarbituric acid (2 mmol), acetate
ammonium (1 mmol), and H2O (5 mL).

The Fe-MCM-41-IL catalyst with concentration of 20 mg, afforded the best yield of product (Table 2, entry 3). Increasing the
amount of catalyst did not change the yield, whereas reducing the
catalyst amount, signicantly decreased the product yield of the
reaction.
With the optimal conditions, we embarked on an investigation
of the substrate scope of this multi-component process with two
moles of 2-thiobarbituric acid, aromatic aldehydes and ammonium
acetate to afford the desired pyrimidines in high yields. The corresponding results are indicated in Table 3.
In terms of electronic effects, it appears that these reactions are
favored by electron withdrawing groups. Aldehydes with electronwithdrawing groups were more active than the electron-donating
substituents and underwent facile conversion yielding the corresponding pyrimidines in good yield (Table 3). However, the reaction
time of aldehydes with electron-withdrawing groups was shorter
than those of with electron-rich groups due to the lower reactivity
of the later aldehydes. A good linear correlation between values of
log (kX/kH) and the BrowneOkamoto constants (R2 0.99; Fig. 7)
was observed for the competitive reaction of substituted aldehydes
(s p-NO2, p-Cl, p-H, p-Me, and p-OMe) [39]. The resulting

Table 3
Three component synthesis of pyrido[2,3-d:6,5-d]dipyrimidinesa (ael).

Compound

t (min)

Yieldb (%)

a
b
c
d
e
f
g
h
i
j
k
l
m
n

C6H6
4-Cl-C6H4
4-NO2-C6H4
4-Me-C6H4
4-OMe-C6H4
2-NO2-C6H4
2-OMe-C6H4
2-OH-C6H4
2-F-C6H4
3-OMe-C6H4
4-Cl-3-NO2-C6H4
2-Pyrimidinyl
2-hydroxy naphthalenyl
4-CHO-C6H4

40
34
25
46
57
30
40
40
45
40
42
35
35
35

89
91
95
87
84
93
85
82
80
92
87
90
91
89

a
Reaction condition: aldehyde (1 mmol), 2-Thiobarbituric acid (2 mmol), acetate
ammonium (1 mmol), Fe-MCM-41-IL (20 mg) and H2O (5 mL).
b
Isolated yields.

27

Hammett parameter r was 0.32, indicating that the electronwithdrawing groups facilitate the reaction. This nding is in
agreement with the proposed reaction mechanism for synthesis of
pyrimidines as shown in Scheme 2.
According to a plausible mechanism which is outline in Scheme
2, the formation of the pyrimidine derivatives is expected to proceed via initial condensation of aldehyde with 1,3-dimethyl-2amino uracil which is formed through the reaction of a molecule
of 2-thiobarbituric acid and ammonium acetate to yield intermediate I. The second molecule of 2-thiobarbituric acid is added to the
intermediate I via Michael addition to generate intermediate II,
which is then cyclized to the nal product. As shown in Scheme 2,
Fe-MCM-41-IL as a catalyst provides a proton source in all steps of
the synthesis of pyrimidines.
The recycling and recovery of the supported catalysts are a very
important issue from both the practical and environment points of
view. We further explored the reusability of the catalyst in the
model reaction between 4-nitro-benzaldehyde, 2-thiobarbituric
acid and ammonium acetate in the presence of 20 mg of FeMCM-41-IL. Then, the catalyst was simply recycled via attaching an
external magnet after completion the reaction and washed with
hot water, dried under vacuum and reused in a subsequent reaction. The results indicated that this simple separation method could
be repeated for ve consecutive runs and the recovered aqueous
phase containing the Fe-MCM-41-IL catalyst remarkably showed
constant catalytic activity in all the six cycles (Fig. 8).
Also, the total surface acidity for the recyclable catalyst was
determined by sodium hydroxide titration and this measurement
was shown that the pH of recyclable catalyst was with slight
decrease 1.07 that can be equal to loading the 2.09 mmol (H) g1.

3. Conclusion
We successfully developed a novel Fe-MCM-41 supported acidic
IL and used in a facile, one-pot four-component condensation reaction of 2-thiobarbituric acid (2 mol) with aromatic aldehydes and
ammonium acetate to prepare pyrimidine compounds in excellent
yields (up to 95%). Moreover, the catalyst recovery test was performed using an external magnet device, and showed that the
catalyst can be reused several times without a signicant decrease
in its performance and catalytic activity.

Fig. 7. Hammett plots for the synthesis of pyrimidines using Fe-MCM-41-IL as catalyst.

28

H. Naeimi et al. / Microporous and Mesoporous Materials 227 (2016) 23e30

Scheme 2. Proposed mechanism for the multicomponent reaction using Fe-MCM-41-IL catalyst.

4. Experimental section

vibrating sample magnetometer (VSM, Meghnatis Daghigh Kavir


Company, Iran).

4.1. General
All chemicals were purchased from Fluka, Merck and Aldrich
chemical companies. FT-IR spectra were obtained as KBr pellets on
a Perkin-Elmer 781 spectrophotometer and on an impact 400
Nicolet FT-IR spectrophotometer. 1H NMR and 13C NMR were
recorded in CDCl3 and DMSO solvents on a Bruker DRX-400 spectrometer with tetramethylsilane as internal reference. The XRD
patterns were recorded on an X-ray diffractometer (Bruker, D8 ADV
ANCE, Germany) using a Cu-Ka radiation (l 0.154056 nm) in the
range 2q 0.5e5 . The N2 adsorption/desorption analysis (BET)
was performed at 196  C using an automated gas adsorption
analyzer (Tristar 3000, Micromeritics). The surface morphology of
the supported catalyst was studied by scanning electron microscopy. FE-SEM and elemental analysis were carried out using a Jeol
SEM instrument (model-VEGA/TESCAN) combined with an INCA
instrument for energy dispersive X-ray spectroscopy scanning
electron microscopy (EDS-SEM), with scanning electron electrode
at 15 kV. The magnetic property of the catalyst was studied by

4.2. Preparation of ionic liquid functionalized iron-containing


MCM-41 (Fe-MCM-41-IL)
Iron-containing MCM-41 was synthesized under directhydrothermal conditions in the presence of cetyl trimethyl
ammonium bromide (CTAB) as template. In a typical synthesis,
2.24 g of ferric chloride (FeCl3$6H2O) was added to a mixture of
480 mL of distilled water, 1.0 g of CTAB and 3.5 mL of 2 M NaOH
aqueous solution. 5 mL of tetraethyl orthosilicate (TEOS) was subsequently dropped into the homogeneous solution under stirring.
After stirring for 2 h at ambient temperature, the product was
separated by filtration, washed with deionized water, and dried at
100  C. The solid product was collected and calcined at 550  C for
6 h in air. The iron content in Fe-MCM-41 was determined to be
0.002 mmol g1 based on AAS.
To prepare the ionic liquid, the 1,2,3-triazole (1-(4-Phenyl-1H1,2,3-triazol-1-yl)butan-2-ol) was synthesized using a reported
procedure [40] then, to a solution of 1,2,3-triazole (3.4 g, 50 mmol)

H. Naeimi et al. / Microporous and Mesoporous Materials 227 (2016) 23e30


100
95

96

90

95

95

95

94

94

93

85
80
75

% Yield

70
65
60
55
50
45
40
35
30

29

of the product solution. This solution was concentrated to generate


the pure crude product. The solid crude product was recrystallized
from hot ethanol to afford the pyrimidine as a pure product. The
obtained products were conrmed and completely characterized
by physical and spectral data (see the Supporting Information).
5-(pyridine-2-yl)-2,8-dithioxo-2,3,7,8,9,10-hexahydropyrido
[2,3-d:6,5-d]dipyrimidine-4,6(1H,5H)-dione (l). Red powder; mp
280  C dec; IR (KBr) n 3398, 3210, 2881, 1605, 1455, 1533; 1H NMR
(DMSO-d6, 400 MHz) d 6.20 (s, 1H, CH), 7.83 (s, 2H, HeAr), 8.42 (m,
1H, HeAr), 8.6 (s, 1H, NH), 11.84 (s, 4H, NH); 13C NMR (DMSO-d6,
100 MHz) d 32.03, 92.94, 124.86, 126.21, 141.98, 146.83,
158.93,163.41, 174.28; EI-MS (70 ev) m/z (%) 51 (8.31), 77 (23.27),
124 (37.53), 126 (4.96), 228 (100), 352 (3.91), 358 (0.06).
Acknowledgments

25
20
1

Number of recycles
Fig. 8. Recycling of the catalyst.

in dry toluene (50 mL), 3-chloropropyltrimethoxysilane (12.0 mL,


50 mmol) was added and the mixture was reuxed overnight under
a nitrogen atmosphere.
The solvent was removed by rotatory evaporation under
reduced pressure and the product was obtained as an intermediate.
Next step, this intermediate (2.72 g, 10 mmol) was dissolved in
toluene (30 mL). The 1,4-butanesultone was added to the reaction
mixture at room temperature for 8 h to produce the zwitterionic
triazoleneammonium salt. The concentrated H2SO4 (0.54 mL,
10 mmol) was added drop wise into the solution of the above
residue in ethanol (30 mL) over 30 min and the nal mixture was
stirred at 50  C for another 8 h. The nal mixture was evaporated
under reduced pressure to give the ionic liquid as a viscous yellow
liquid. The spectral data for IL is as follows: 1H NMR (400 MHz, D2O)
d 8.05 (s, 1H), 7.07 (d, 1H), 6.88 (m, 3H), 3.88 (m, 2H), 3.39 (s, 4H),
2.95 (s, 9H) 2.59 (m, 2H), 1.50 (m, 2H), 1.16 (m, 2H), 0.57 (m, 3H),
0.46 (m, 2H); 13C NMR (100 MHz, D2O) d 140.61, 129.65, 127.55,
124.62, 120.11, 74.04, 64.09, 56.47, 56.14, 45.78, 20.59, 20.11, 14.17,
14.10, 12.13, 7.15.
For immobilization of IL onto Fe-MCM-41, the solution of IL
(containing 0.3 g IL) was diluted with dry CHCl3 and was then added
slowly to a suspension of 1 g hydrated Fe-MCM-41 in dry CHCl3
(180 mL), under argon atmosphere. The resulting mixture was
reuxed for 24 h. After cooling, the solid materials were ltered off
and the residue was washed with hot CHCl3 and then dried in oven at
90  C overnight to give IL matrix immobilized on Fe-MCM-41.
A 0.08 M solution of sodium hydroxide was used for measurement of total surface acidity for the Fe-MCM-41-IL and Fe-MCM-41.
Then, 0.02 g of solid was suspended in this solution for 24 h, and the
excess amount of base was titrated against hydrochloric acid using
phenolphthalein as an indicator.
4.3. General procedure for the synthesis of pyrimidine derivatives
using Fe-MCM-41-IL as a catalyst
An equimolar mixture of benzaldehyde (1 mmol), 2thiobarbituric acid (2 mmol), ammonium acetate (1 mmol) and
20 mg Fe-MCM-41-IL in H2O (5 mL) was stirred at room temperature for 30 min. The progress of the reaction was monitored by TLC.
After completion of reaction, the reaction mixture was ltered.
Then, the product was dissolved in mixture of water/ethanol and
the catalyst easily separated from the product by attaching an
external magnet onto the reaction vessel, followed by decantation

The authors are grateful to University of Kashan for supporting


this work by Grant No. 159148/52.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.micromeso.2016.02.036.
References
[1] J. Choma, M. Jaroniec, W. Burakiewicz-Mortka, M. Kloske, Appl. Surf. Sci. 196
(2002) 216.
[2] C.T. Kresge, M.E. Leonowicz, W.J. Roth, J.C. Vartuli, J.S. Beck, Nature 359 (1992)
710.
[3] J.S. Beck, K.D. Schmitt, J.B. Higgins, J.L. Schlenkert, J. Am. Chem. Soc. 114 (1992)
10834.
[4] C. Cheng, W. Zhou, J. Klinowski, Chem. Phys. Lett. 4 (1996) 2.
[5] A. Corma, Chem. Rev. 97 (1997) 2373.
[6] R. Savidha, A. Pandurangan, M. Palanichamy, V. Murugesan, J. Mol. Catal. A
Chem. 211 (2004) 165.
[7] M. Stockenhuber, M.J. Hudson, R.W. Joyner, J. Phys. Chem. B 104 (2000) 3370.
[8] P.B. Amama, S. Lim, D. Ciuparu, Y. Yang, L. Pfefferle, G.L. Haller, J. Phys. Chem. B
(2005) 2645.
[9] J.-S. Choi, S.-S. Yoon, S.-H. Jang, W.-S. Ahn, Catal. Today 111 (2006) 280.
[10] M. Esther Leena Preethi, S. Revathi, T. Sivakumar, D. Manikandan, D. Divakar,
A. Valentine Rupa, M. Palanichami, Catal. Lett. 120 (2007) 56.
[11] N. Gokulakrishnan, A. Pandurangan, P.K. Sinha, Ind. Eng. Chem. Res. 48 (2009)
1556.
[12] R. Huang, B. Lan, Z. Chen, H. Yan, Q. Zhang, J. Bing, L. Li, Chem. Eng. J. 180
(2012) 19.
[13] D. Pinkert, C. Limberg, Chem. Eur. J. 20 (2014) 9166.
[14] A. Wingen, N. Anastasievi
c, A. Hollnagel, D. Werner, F. Schth, J. Catal. 193
(2000) 248.
[15] C. Wu, Y. Kong, F. Gao, Y. Wu, Y. Lu, J. Wang, L. Dong, Microporous Mesoporous Mater. 113 (2008) 163.
[16] S.V. Sirotin, I.F. Moskovskaya, B.V. Romanovsky, Catal. Sci. Technol. 1 (2011)
971.
[17] R. Sheldon, Chem. Commun. (2001) 2399.
[18] P. Wasserscheid, W. Keim, Angew. Chem. Int. Ed. 39 (2000) 3772.
[19] S. Das, T. Asefa, ACS Catal. 1 (2011) 502.
ro
^ me, J. Barrault, Org. Lett. 9 (2007) 3145.
[20] Y. Gu, A. Karam, F. Je
[21] D.A. Links, Chem. Commun. (2012) 3327.
[22] C.P. Mehnert, R.A. Cook, N.C. Dispenziere, M. Afeworki, J. Am. Chem. Soc. 124
(2002) 12932.
[23] C.P. Mehnert, J. Mozeleski, R.A. Cook, Chem. Commun. (2002) 3010.
[24] J. Xiong, W. Zhu, H. Li, Y. Xu, W. Jiang, S. Xun, H. Liu, Z. Zhao, C. R. Chim. 59
(2013) 4696.
[25] A. Khala-Nezhad, S. Mohammadi, ACS Comb. Sci. 15 (2013) 512.
[26] A. Bazgir, M.M. Khanaposhtani, R. Ghahremanzadeh, A.A. Soorki, C. R. Chim. 12
(2009) 1287.
[27] M. Kawase, A. Shah, H. Gaveriya, N. Motohashi, H. Sakagami, A. Varga,
J. Molnar, Bioorg. Med. Chem. 10 (2002) 1051.
[28] A. Boumendjel, D. Baubichon-Cortay, H. Trompier, T. Perrotton, A. Di Pietro,
Med. Res. Rev. 25 (2005) 453.
[29] A. Agarwal, Ramesh, Ashutosh, N. Goyal, P.M.S. Chauhan, S. Gupta, Bioorg.
Med. Chem. 13 (2005) 6678.
[30] W. Jie-Ping, L. Yunyun, Rsc Adv. 2 (2012) 9763.
[31] A. Hantzsch, Justus Liebigs Ann. Chem. 1 (1892) 215.
[32] B. Guillaume, A.B. Charette, J. Am. Chem. Soc. 130 (2008) 18.
[33] M. Kidwai, R. Mohan, S. Saxena, Russ. Chem. Bull. Int. Ed. 52 (2003) 2457.
[34] G.-W. Wang, C.-B. Miao, Green Chem. 8 (2006) 1080.

30

H. Naeimi et al. / Microporous and Mesoporous Materials 227 (2016) 23e30

[35] Y. Jiang, K. Lin, Y. Zhang, J. Liu, G. Li, J. Sun, X. Xu, Appl. Catal. A 445e446
(2012) 172.
[36] H. Kosslick, G. Lischke, G. Walther, W. Storek, a. Martin, R. Fricke, Microporous
Mesoporous Mater. 9 (1997) 13.

[37] Li Baoshan, K. Wu, T. Yuan, C. Han, J. Xu, X. Pang, Microporous Mesoporous


Mater. 151 (2012) 277.
[38] G. Leofanti, M. Padovan, G. Tozzola, B. Venturelli, Catal. Today 41 (1998) 207.
[39] H.C. Brown, Y. Okamoto, J. Am. Chem. Soc. 80 (1958) 4979.
[40] H. Naeimi, V. Nejadshaee, New J. Chem. 38 (2014) 5429.

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