Beruflich Dokumente
Kultur Dokumente
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.
24
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
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.
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.
26
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
Fe-MCM-41
Fe-MCM-41-IL
307.98
225
8.42
8.25
0.42
0.38
a
b
c
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
Scheme 2. Proposed mechanism for the multicomponent reaction using Fe-MCM-41-IL catalyst.
4. Experimental section
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
96
90
95
95
95
94
94
93
85
80
75
% Yield
70
65
60
55
50
45
40
35
30
29
25
20
1
Number of recycles
Fig. 8. Recycling of the catalyst.
30
[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.