CuO supported 1-methyl-3-(3-(trimethoxysilyl) propyl) imidazolium chloride (MTMSP-Im/Cl) nanoparticles as an efficient simple heterogeneous catalysts for synthesis of β-azido alcohols

Article abstract of DOI:10.1007/s13738-019-01623-4

In the present study, CuO supported 1-methyl-3-(3-(trimethoxysilyl) propyl) imidazolium chloride (MTMSP-Im/Cl) is synthesized as a novel, efficient and eco-friendly heterogeneous nanocatalyst. This nanocatalyst was applied for selective ring opening of ep

Full text of DOI:10.1007/s13738-019-01623-4

Journal of the Iranian Chemical Society
https://doi.org/10.1007/s13738-019-01623-4
ORIGINAL PAPER
CuO supported 1-methyl-3-(3-(trimethoxysilyl) propyl) imidazolium
chloride (MTMSP-Im/Cl) nanoparticles as an efficient simple
heterogeneous catalysts for synthesis of β-azido alcohols
E. Fadavipoor1,2 · R. Badri1,2 · A. Kiasat · H. Sanaeishoar1,2
3
Received: 10 May 2018 / Accepted: 29 January 2019
©
Iranian Chemical Society 2019
Abstract
In the present study, CuO supported 1-methyl-3-(3-(trimethoxysilyl) propyl) imidazolium chloride (MTMSP-Im/Cl) is
synthesized as a novel, efficient and eco-friendly heterogeneous nanocatalyst. This nanocatalyst was applied for selective
ring opening of epoxides with azide anion in water. Structure and morphology of the obtained catalyst were investigated by
FT-IR spectroscopy, XRD, TGA, FE-SEM, and EDX techniques. All the results confirmed that MTMSP-Im/Cl is grafted
on to CuO nanoparticles. The synthesized nanohybrid can be easily separated after completion of the reaction and reused
for four cycles without any significant reduction of its catalytic activity.
Keywords Heterogeneous nanocatalyst · Ring opening of epoxides · β-azido alcohols · CuO nanoparticles
Introduction
are of special interest, because CuO has been shown to be
an industrially important material that can be widely used
in various applications such as gas sensor, magnetic storage
media, battery, diode, solar energy transformation, nano-
fluid, semiconductor, and heterogeneous catalysis [5–12].
β-azido alcohols are remarkably versatile class of com-
pounds which are very important in organic chemistry due to
their pharmaceutical and industrial applications and useful
precursors for the synthesis of oxazolines, lactames, amino
sugars, and carboxylic nucleosides [13]. Various catalysts
have been reported for the synthesis of β-azido alcohols in
the presence of azide anion under mild conditions [14–29].
Although some of the reported catalysts give good yields
under mild conditions, for the ring opening of epoxides,
most of them are not environmentally friendly and suffer
from high toxicity, tedious work up, used of expensive met-
als, or the need for large amounts of catalyst and difficulty
in recovery and reusability of it [30–34]. Therefore, the
development of clean, high-yielding, and environmentally
friendly approaches is still a challenge for organic chemists
in the synthesis of β-azido alcohol derivatives.
Nowadays, many organic reactions are carried out in the
presence of catalysts. Heterogenization of homogeneous
catalysts has been an interesting area of research from the
industrial point of view; this combines the advantages of
homogeneous catalysts (high activity and selectivity, etc.)
with the engineering advantages of heterogeneous catalysts
such as easy catalyst separation, long catalytic life, easy cat-
alyst regenerability, thermal stability, and recyclability [1].
Among heterogeneous catalysts, CuO nanoparticles’
(
NPs) materials containing high surface area and reactive
morphologies have been used widely as an efficient catalyst
for organic synthesis due to good chemical and thermal sta-
bility, low cost, low toxicity, ease of handling, and high cata-
lytic activity reusability [2–4]. Copper oxide nanoparticles
*
R. Badri
rashidbadri@scu.ac.ir; rashidbadri@yahoo.com
1
Department of Chemistry, College of Science, Khuzestan
Science and Research Branch, Islamic Azad University,
Ahvaz, Iran
Based on the above introduction, in this work, we
reported a new functionalized CuO nanoparticle with
1-methyl-3-(3-trimethoxysilylpropyl)-imidazolium chloride
to obtain a heterogeneous catalyst for the regioselective for-
mation of a variety of β-azido alcohols from epoxides under
mild conditions.
2
3
Department of Chemistry, College of Science, Ahvaz Branch,
Islamic Azad University, Ahvaz, Iran
Chemistry Department, College of Science, Shahid Chamran
University of Ahvaz, Ahvaz, Iran
Vol.:(0
1
123456789)
3

Journal of the Iranian Chemical Society
Experimental part
MeO
MeO Si
MeO
N
N
General
Cl
Nano-CuO powder was purchased from Alborz Chemi-
cal Co. (Tehran, Iran). Nano-size CuO powder had
average particle size of < 50 nm and specific surface
2
−1
areas > 80 m g . Other chemical reagents in high purity
were purchased from Merck and Aldrich and were used
without further purification. Products were characterized
EtOH, r.t, 24h
Ultrasonic 2h
Filtration
1
13
by comparison of their physical data, FT-IR, H, and
C
NMR spectra with the known samples [21, 35–38]. The
purity of the compounds synthesized was monitored by
TLC on silica gel polygram SILG/UV 254 plates.
1
13
H NMR (400 MHz) and C NMR (100 MHz) spectra
HO
OH
were recorded on a Bruker Avance DPX 400 MHz spec-
trometer, respectively. An FT-IR spectrum of the CuO-
np@MSP-Im/Cl nanocatalyst and products were recorded
HO
HO
O
O
O
CuO
HO
Si
N
N
HO
Cl
−
1
in the range 400–4000 cm on a Perkin-Elmer 550 spec-
trometer. The particle size, external morphology of the
particles, and elemental analysis of the nanocatalyst were
characterized by field-emission scanning electron micros-
copy (FE-SEM) and energy-dispersive X-ray (EDX) spec-
troscopy, model Mira 3-XMU. X-ray diffraction (XRD)
patterns of the samples were taken on a Philips X-ray
diffractometer Model PW1840. The thermal gravimetric
analysis (TGA) curve of the heterogeneous nanocata-
lyst was recorded on BAHR SPA 503 at heating rates of
Scheme 1 Surface-functionalized CuO nanoparticles
CuO nanoparticles were dried under vacuum for 24 h
and were grounded with a mortar and pestle before use
(
Scheme 1). The presence of organic groups on the surface
of functionalized nanoparticles was confirmed by FT-IR,
TGA, XRD, EDX, and FE-SEM analysis.
−
1
1
0 °C min . Modification CuO (NPs) was carried out
on ultrasonic liquid processor. Ultrasound was wave of
General procedure for the regioselectivity of ring
opening of epoxides by CuO‑np@MSP‑Im/Cl
heterogeneous nanocatalyst
4
frequency 2.25 × 10 Hz and power of 100W.
Preparation of CuO‑np@MSP‑Im/Cl catalyst
A mixture of epoxide (1 mmol), sodium azide (2 mmol), and
catalyst (0.08 g) in water (5 ml) was stirred at 80 °C for the
time as shown in Table 4. The completion of the reaction
was followed by TLC using n-hexane/ethyl acetate (5/1) as
eluent. The reaction mixture was filtrated, and separated cat-
alyst dried and regenerated. Then, the product was extracted
with diethyl ether (3 × 5 mL), and the organic phase was
In the first step, 1-methyl-3-(3-(trimethoxysilyl) propyl)
imidazolium chloride (MTMSP-ImCl) was prepared
according to the reported method valizadeh [39]. The
product was identified through the spectroscopic data,
which were confirmed by comparison with those reported
in the literature [40]. In the second step, MTMSP-Im/
Cl was dissolved in deionized water and stirred at room
temperature for15 min, and then, the mixture was ultra-
sonicated for 15 min (A). In the following, CuO nano-
powders were suspended in the deionized (DI) water and
the obtained mixture was ultrasonicated for 15 min (B).
Then, solutions A and B were mixed and immersed in eth-
anol and slowly stirred at room temperature for 24 h, and
then ultrasonicated for 2 h. Finally, the reaction mixture
was filtered using Whatman filter paper and, subsequently,
was washed with deionized water two times to remove the
unattached coupling agent compound. The functionalized
concentrated and dried using MgSO . After evaporation of
4
the solvent under reduced pressure with a rotary evaporator,
the β-azido alcohols were obtained with high yields. The
desired pure product(s) were identified on the basis of their
1
13
IR, H NMR, and C NMR.
Selected spectral data
1
-Azido-3-phenoxy-2-propanol (Table 4, entry 1): IR
1
(
neat): ν
N (2110), OH (3395). H NMR (400 MHz,
max
3
CDCl ) δ 3.45–3.54 (m, 2H), 3.89 (m, 1H), 3.97–4.03 (m,
3
2
H), 4.18 (s, 1H), 6.95-7.00 (m, 2H), 7.02–7.06 (m, 1H),
1
3

Journal of the Iranian Chemical Society
7
6
.27–7.36 (m, 2H); 13C NMR (100 MHz, CDCl ): δ 52.3,
3
7.1, 68.3, 112.7, 120.1, 128.8, 157.9.
1
-Azido-3-allyloxy-2-propanol (Table 4, entry 2): IR
1
(
neat): ν
N (2100), OH (3400). H NMR (400 MHz,
max
3
CDCl ): δ 3.41–3.49 (m, 2H), 3.8 (m, 1H), 3.96–4.04 (m,
3
2
5
7
H), 4.18 (s, 1H), 3.5 (m, 2H), 5.2 (dd, 1H), 5.5 (dd, 1H),
1
3
.9 (dd, 1H); C NMR (100 MHz, CDCl ): δ 53.39, 69.85,
3
1.30, 72.09, 117.33, 134.35.
1
-azido-2-octanol (Table 4, entry 5): IR (neat): ν
N
max 3
1
(
2104), OH (3404). H NMR (400 MHz, CDCl ): δ 0.78
3
(
t, J=6.2 Hz, 3H), 1.20 (s, 7H), 1.35 (s, 3H), 1.95 (s, 1H),
1
3
3
.16–3.32 (m, 2H), 3.65 (s, 1H); C NMR (100 MHz,
CDCl ): δ 12.12, 20.01, 23.45, 27.21, 30.56, 33.41, 55.17,
3
Fig. 1 FT-IR spectra of a bare CuO and b CuO-np@MSP-Im/Cl
6
9.74.
nanohybrid
2
-Azido-2-phenyl-1-ethanol (Table 4, entry 11): IR
1
(
neat): ν
N (2096), OH (3405). H NMR (400 MHz,
max
3
CDCl ): δ 2.60 (s, 1H), 3.72–3.84 (m, 2H), 4.64 (t, 1H
FT-IR analysis was employed to study the formation of
the heterogeneous catalyst. Figure 1 shows FT-IR spec-
tra of pure CuO and CuO-np@MSP-Im/Cl nanoparticles.
3
1
3
J = 6.7 Hz), 7.30–7.61 (m, 5H); C NMR (100 MHz,
CDCl ): δ 65.5, 67.5, 125.6, 126.9, 128.8, 136.1.
3
Results and discussion
The application of CuO nanoparticles for organic reactions
has attracted much attention in the recent years [41–46].
However, since, the bare CuO NPs are not soluble in
organic solvents or water and easily aggregated, the pres-
ence of organic groups within the inorganic materials helps
effectively to increase the hydrophobicity and hydrother-
mal behavior of these materials as well as decrease their
tendency to agglomerate [47, 48]. Considering these facts,
herein, we reported the synthesis of a new nanocatalyst of
CuO NPs that are modified with an ionic liquid-containing
imidazolium group (Scheme 1). This new catalyst which is
easily dispersed in the water or polar organic phase is a solid
acid and was used to promote the epoxides azidolysis under
very mild condition (Scheme 2). The chemical structure of
CuO-np@MSP-Im/Cl nanohybrid was characterized using
FT-IR, TGA, XRD, EDX, and FE-SEM analysis.
Fig. 2 XRD pattern a pure CuO NPs and b CuO-np@MSP-Im/Cl
nanohybrid
PhOCH2
HO
H
O
N3
O
HO
HO
O
O
CuO
Si
N
N
O
+
HO
Cl
HO
Na
Scheme 2 Postulated roles of CuO-np@MSP-Im/Cl nanohybrid in
the β-azido alcohol synthesis
Fig. 3 TGA curve CuO-np@MSP-Im/Cl nanocatalyst
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Journal of the Iranian Chemical Society
In the spectrum of bare CuO nanoparticles (Fig. 1a), the
to the presence of C–H vibration, and the absorption at
−
1
−1
peak at 529.48 cm is attributed to Cu–O bond stretch-
3077.37 cm is due to remaining hydroxyl groups on NPs’
−
1
ing. The broadband peak in region 3431 cm shows the
O–H-stretching vibration of surface hydroxyls. The band at
surface. These results provided the evidences that MTMSP-
Im/Cl (coupling agent) were successfully attached to the
surface of CuO NPs.
−
1
1
621 cm is the O–H-bending vibrations. The spectrum
(
(
Fig. 1b) shows the modified CuO NPs with ionic liquid
MTMSP-Im/Cl). The hydroxyl stretching and bending
The crystalline structures of samples at room tempera-
ture were examined using a Philips X-ray diffractometer
equipped with a Cu Kα anode (λ =1.540 Å) for 2θ, in the
range of 10°–90°. The XRD patterns of bare CuO and CuO-
np@MSP-Im/Cl nanohybrid are presented in Fig. 2. The
diffraction lines in Fig. 2a can be assigned to single-phase
CuO with a monoclinic structure [49]. In the XRD pattern of
Fig. 2b, the presence of MTMSP-Im/ Cl is observed in addi-
tion to CuO, and reflections of monoclinic CuO phase were
clearly observed in surface-modified NPs. This observation
−
1
bands are shifted to 3416 and 1635 cm respectively. The
−
1
new bands at 1383 and 1059 cm can be attributed to the
attached IL on the surface of CuO NPs. The strong peak
−
1
appeared at 525.48 cm was assigned to Cu–O-stretching
−
1
vibration. The broadband at 1059 cm refers to the pres-
ence of (Si–O–Si) stretching vibration. The two broad peeks
−
1
−1
at 1683.09 cm and 1507.39 cm are related to C=N and
C=C vibrations, the new band at 2885 cm− attributed
1
Fig. 4 FE-SEM image of a original CuO NPs and b, c CuO-np @MSP-Im/Cl nanocatalyst
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Journal of the Iranian Chemical Society
confirms the nanohybrid formation of interaction between
MTMSP-Im/Cl and CuO nanoparticles. The crystal size of
nanohybrid is 18–45 nm as determined by Debby-Sherrer’s
formula.
photographs of the surface bare CuO NPs and CuO-np@
MSP-Im/Cl hybrid. As shown, the synthesized heterogene-
ous nanocatalyst has needle shape with nano-thickness rang-
ing from 10 to 50 nm and with nano-needle length ranging
from 1 to 2µm.
TGA of solid acidic CuO-np@MSP-Im/Cl heterogeneous
catalyst and the amount of the loading MTMSP-Im/Cl were
investigated by thermal gravimetric analysis (Fig. 3) and
Volhard’s method. The 17% weight loss below 150 °C might
be due to the loss of the adsorbed water as well as dehy-
dration of the surface –OH groups. At higher temperature
around 246–800 °C, it seems that the organic part is decom-
posed by a mass loss of about 12%. Thus, the TGA curves
also convey the obvious information that the MTMSP-Im/Cl
molecules are successfully immobilized onto CuO NPs. The
amount of chloride that is equal by imidazolium units was
The corresponding energy-dispersive X-ray (EDX) spec-
troscopy measurements are tabulated in Table 1. The result
confirmed the presence of expected elements in the structure
of the catalyst, namely Cu, C, N, Si, Cl, and O. Therefore,
the structure of the catalyst was completely confirmed by
EDX analysis.
After successful characterization of CuO-np@MSP-
Im/Cl catalyst, we have tested its catalytic activity for the
synthesis of β-azido alcohols derivatives by reaction of
different epoxides with sodium azide. In the beginning, a
model reaction of 3-phenoxy-1, 2-epoxypropane (1 mmol)
and sodium azide (2–3 mmol) in the presence of CuO-np@
MSP-Im/Cl Catalyst was investigated in various conditions,
and compared with the other catalysts. The results obtained
−
1
also determined by Volhard’s method [50] (0.38 mmol g ).
The FE-SEM scanning electron microscopy images were
used to obtain the surface morphology, size distribution, and
particles shape of modified CuO NPs. Figure 4 shows the
Table 1 EDX of bare CuO and
Sample
Compound (at%)
CuO-np@MSP-Im/Cl samples
C
Cu
O
N
Cl
Si
Bare CuO NPs
CuO-np@MSP-Im/Cl
31.62
20.48
68.38
49.53
19.89
4.30
3.71
2.09
Table 2 Optimization of
reaction conditions for
ring-opening 3-phenoxy-1,
Entry
Catalyst (g)
NaN
Temperature Solvent
(°C)
Time (min)
Yield%
3
(
mmol)
2
-epoxypropane
1
2
3
4
5
6
7
8
9
–
0.08
0.08
0.08
0.12
0.08
0.08
0. 08
3
2
3
2
2
2
2
3
2
80
80
80
80
80
80
80
80
80
H O
–
120
50
20
20
25
40
40
30
130
Trace
67
85
96
88
70
73
80
54
2
H O
2
H O
2
H O
2
CH OH
3
C H OH
2
5
CH CN
3
0.08 bare CuO
H O
2
Table 3 Comparison of
Entry
Catalyst/g
Time (min)
Yield%
References
azidolysis of 3-phenoxy-1,
2
-epoxypropane with different
1
2
3
4
5
6
7
8
Fe O @SiO /BNC/0.03
50
55
60
35
60
120
90
20
95
94
90
99
80
95
89
96
[51]
[18]
[52]
[21]
[53]
[54]
[29]
This work
3
4
2
catalysts
[Hmim] N /3 mmol
PEG-300/2
3
Fe O –PS–Co–[PAA–g–PEG]/0.01
3
4
TSIL-N /2 mmol
3
SiO –PEG/0.1
2
Network polymer/0.1
CuO-np@MSP-Im/Cl/0.08
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Journal of the Iranian Chemical Society
Table 4 CuO-np@MSP-Im/Cl catalyzed regioselective ring opening of epoxides
a
b
Entry
Epoxide
Product(s)
HO
Time(min)
Yields(%)
O
1
PhOCH2
20
45
96
91
PhOCH2
N3
HO
O
2
CH =CHCH OCH
2
2
2
CH =CHCH OCH
2
N3
2
2
O
HO
CH ) CHOCH
2
3
4
20
15
85
93
90
(
CH ) CHOCH
3 2 2
N3
(
3
2
O
OH
N3
O
OH
N3
5
6
28
27
O
HO
CH (CH ) CH OCH
3
2 2
2
2
81
90
CH (CH ) CH OCH
2
N3
3
2 2
2
O
OH
40
N3
7
N3
O
8
9
45
25
78
OH
N3
120
O
OH
OH
1
0
1
70
25
90
86
O
N3
O
N3
1
Ph
OH
Ph
a
Products were identified by comparison of their physical and spectral data with those of authentic samples
Isolated yields
b
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Journal of the Iranian Chemical Society
Fig. 5 Recyclability of the
CuO-np@MSP-Im/Cl heteroge-
neous catalyst
are summarized in Tables 2 and 3. After some experiments,
it was found that the use of 2 mmol of sodium azide per
and simple workup in isolation of the products with high
purity.
3
-phenoxy-1, 2-epoxypropane in the presence of CuO-np@
Acknowledgements We are grateful acknowledge support of the
MSP-Im/Cl (0.08 g) in water was the best condition (Table 2
entry 4). As shown in Table 2, the higher activity of the
immobilized catalyst CuO-np@MSP-Im/Cl compared with
its bare CuO NPs could be attributed to the participation of
MTMSP-Im/Cl in the catalytic process (compared entries 4
and 9). As can be seen in Table 3, higher yield and shorter
reaction time of product were obtained when CuO-np@
MSP-Im/Cl was utilized as the catalyst (entry 9). Therefore,
this reaction was developed with a wide range of substituted
epoxides with sodium azide in the presence of synthesized
heterogeneous nanocatalyst under mild conditions and the
results are summarized in Table 4. These results clearly
demonstrate that CuO-np@MSP-Im/Cl is an efficient cata-
lyst for the high regioselectivity of ring opening of epoxides.
Due to the importance of green chemistry and catalyst
recycling, of CuO-np@MSP-Im/Cl nanohybrid was inves-
tigated under the optimized conditions. The catalyst was
reused four times in the one-pot 3-phenoxy-1, 2-epoxy pro-
pane with sodium azide in water. The recovered catalyst was
reused after each run, washed with water and ethanol, and
dried in an oven at 60 °C for 30 min. The results illustrated
in Fig. 5 showed that the catalyst CuO-np@MSP-Im/Cl was
reused with consistent activity even after the four cycles.
research by the Ahvaz branch of Islamic Azad University.
References
1. F. Shirini, M. Abedini, J. Nanosci. Nanotechnol. 13, 4838 (2013)
2
.
L. Rout, T.K. Sen, T. Punniyamurthy, Angew. Chem. 46, 5583
(
2007)
3
.
L. Rout, S. Jammi, T. Punniyamurthy, Org. Lett. 9, 3397 (2007)
4. M. Nasrollahzadeh, M. Maham, S.M. Sajadi, J. Colloid Interface
Sci. 455, 245 (2015)
5
6
.
.
S. Rahimnejad, S. Rahman Setayesh, M.R. Gholami, J. Iran.
Chem. Soc. 5, 367 (2008)
Y.P. Sukhorukov, N.N. Loshkareva, A.A. Samokhvalov, S.V. Nau-
mov, A.S. Moskvin, A.S. Ovchinnikov, J. Magn. Mater. 183, 356
(1998)
7
8
.
.
M. Frietsch, F. Zudock, J. Goschnick, M. Bruns, Sens. Actuators
B 65, 379 (2000)
C.L. Carnes, K.J. Klabunde, J. Mol. Catal. A 194, 227 (2003)
9. P. Dai, H.A. Mook, G. Aeppli, S.M. Hayden, F. Dogan, Nature.
406, 965 (2000)
1
0. E. Rakhshani, F.K. Barakat, Mater. Lett. 6, 37 (1987)
1
1. D. Arun Kumar, F.P. Xavier, J.M. Shyla, Appl. Sci. Res. 4, 2174
(
2012)
12. E. Darezereshki, F.J. Bakhtiari, Min. Metall. Sect. B Metall. 47,
73 (2011)
1
1
3. S.W. Chen, S.S. Thakur, W. Li, C.K. Shin, R.B. Kawthekar, G.J.
Kim, J. Mol.Catal. A Chem. 259, 116 (2006)
4. F. Kazemi, A.R. Kiasat, S. Ebrahimi, Synth. Commun. 33, 999
(2003)
Conclusion
1
1
5. B. Yadollahi, H. Danafar, Catal. Lett. 113, 120 (2007)
6. G. Sabitha, R.S. Babu, M.S.K. Reddy, J.S. Yadav, Synthesis 15,
In this work, CuO supported 1-methyl-3-(3-
2
254 (2002)
(
trimethoxysilyl) propyl) imidazolium chloride (CuO-np@
1
7. S. Sajjadifar, Z. Abbasi, E. Rezaee Nezhad, M.Rahimi
Moghaddam, S. Karimian, S. Miri, J. Iran. Chem. Soc. 11, 335
(2014)
MSP-Im/Cl) was successfully synthesized under ultrasonic
irradiation. Then, the synthesized catalyst showed good
performance in the synthesis of β-azido alcohols. The
catalyst can easily be separated by simple filtration and
reused for several cycles with consistent activity. Moreo-
ver, this methodology offers several advantages, including
excellent regioselectivity, high yields, short reaction times,
1
1
8. F. Heidarizadeh, A.BeitSaeed,E.C.R. Rezaee-Nezhad, Chimie 17,
4
50 (2014)
9. G. Sabitha, R.S. Babu, M. Rajkumar, J.S. Yadav, Org. Lett. 4, 343
(2002)
20. M. Chini, P. Crotti, F. Macchia, Tetrahedron Lett. 31, 5641 (1990)
2
1. R. Kiasat, M. Daei, S.J. Saghanezhad, Res. Chem. Intermed. 42,
81 (2016)
5
1
3

Journal of the Iranian Chemical Society
2
2. S. Saito, S. Yamashita, T. Nishikawa, Y. Yokoyama, M. Inaba, T.
Moriwake, Tetrahedron Lett. 30, 4153 (1989)
39. H. Valizadeh, M. Amiri, F. Hossenzadeh, Dyes Pigment. 92, 1308
(2012)
2
2
3. M. Onaka, K. Sugita, Y.J. Izumi, Org. Chem. 54, 1116 (1989)
4. B. Mombani Godajdar, A.R. Kiasat, M.J. Mahmoodi, Hashemi,
Mol. Liq. 183, 14 (2013)
40. S. Chrobok, W. Baj, A. Pudlo, Appl. Catal. A Gen. 366, 22 (2009)
41. K. Yamamoto, T. Kasuga, M. Nogami, Electrochem. Solid-State
Lett. 2, 595 (1999)
2
5. F. Benedetti, F. Berti, S. Norbedo, Tetrahedron Lett. 39, 7971
42. P. Poizot, S. Laruelle, S. Grugeon, L. Dupont, J.M. .Tarascon,
Nature. 407, 496 (2000)
(
1998)
2
2
6. N. Iranpoor, F. Kazemi, Synth. Commun. 29, 561 (1999)
43. Y. Liu, Q. Fu, M.F. Stephanopoulos, Catal. Today 93, 241 (2004)
44. X. Jiang, L. Lou, Y. Chen, X. Zheng, Catal. Lett 94, 49 (2004)
45. A.B. Martinez-Arias, M. Hungria, J.C. Fernandez-Garcia, G.
Conesa, Munuera, J. Phys. Chem. B 108, 17983 (2004)
46. V.P. Reddy, A.V. Kumar, K. Swapna, K.R. Rao, Org. Lett. 11, 951
(2009)
7. S. Rezayati, E. Rezaee Nezhad, R. Hajinasiri, Chin. Chem. Lett.
2
7, 974 (2016)
2
2
8. M. Kamal, M.V. Arifuddin, Rao, Tetrahedron Asymmetry 10,
261 (1999)
9. A.R. Mouradzadegun, P. Kiasat, Kazemian, Fard, Catal. Commun.
4
2
9, 1 (2012)
47. G. Faure, A. Salazar-Alvarez, G. Ahniyaz, Y. Villaluenga, R.D.
Berriozabal, L. Miguel, Sci Technol Adv Mater. 14, 023001
(2013)
3
3
0. M. Chini, P. Crotti, F. Macchia, Tetrahedron Lett. 31, 5641 (1999)
1. M. Chini, P. Crotti, L.A. Fli ppin, C. Gardelli, E. Giovani, F. Mac-
chia, M. Pineschi, J. Org. Chem. 58, 1221 (1993)
48. H. Keller, D. Wang, H.S. Zhou, B.J. Lenihan, G. Cherr, R. Cardi-
nale, Z. Miller, Sci Technol 44, 1962 (2010)
3
3
3
2. P. Serrano, A. Llebaria, A. Delgado, J. Org. Chem. 70, 7829
(
2005)
49. M. Sahooli, S. Sabbaghi, R. Saboori, Mater. Lett. 81, 169 (2012)
50. Sivasankar B Engineering chemistry Tata McGraw-Hill Pub.
Co.Ltd, New Delhi (2008)
3. P. Crotti, V. Di Bussolo, L. Favero, F. Macchia, M. Pineschi, Tet-
rahedron Lett. 37, 1675 (1996)
4. S.S. Palimkar, S.A. Siddiqui, T. Daniel, R.J. Lahoti, K.V. Srini-
vasan, J. Org. Chem. 68, 9371 (2003)
51. R. Kiasat, F. Chadorian, S.J. Saghanezhad, C. R. Chimie. 18, 1297
(2015)
3
3
5. M. Hosseini-Sarvari, G. Parhizgar, Org. Chem. Res. 2, 177 (2016)
6. R. Kiasat, R. Mirzajani, H. Shalbaf, T.Tabatabaei,M. Fallah-
Mehrjardi, J. Chin. Chem. Soc. 56, 594 (2009)
52. R. Kiasat, M. Fallah-Mehrjardi, J. Iran. Chem. Soc. 6, 542 (2009)
53. S. Fadavipoor, S. Nazari, M. Saadat, J. Chem. Soc. Pak. 34, 6
(2012)
3
3
7. M. Onaka, K. Sugita, Y. Izumi, J.Org.Chem. 54, 1116 (1989)
8. R.N. Reddi, A. Sudalai, Chem. Commun. 51, 10276 (2015)
54. R. Kiasat, M. Zayadi, Catal. Commun. 9, 2063 (2008)
1
3