Co3O4-decorated carbon nanotubes as a novel efficient catalyst in the selective oxidation of benzoins

Article abstract of DOI:10.1016/j.crci.2013.09.003

An efficient and facile air oxidation of benzoins in the presence of the heterogeneous catalyst, Co₃O₄-CNTs nanocomposite, has been developed. It thus constitutes a very simple, clean, economical and selective method for the aerobic preparation of benzils from the corresponding benzoins. The catalyst can be re-used a number of times without losing its catalytic activity to a greater extent.

Full text of DOI:10.1016/j.crci.2013.09.003

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´
Full paper/Memoire
Co3O4-decorated carbon nanotubes as a novel efficient
catalyst in the selective oxidation of benzoins
*
Javad Safari , Zahra Mansouri Kafroudi, Zohre Zarnegar
Laboratory of Organic Compound Research, Department of Organic Chemistry, College of Chemistry, University of Kashan, PO Box: 87317-
51167, Kashan, 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:
An efficient and facile air oxidation of benzoins in the presence of the heterogeneous
catalyst, Co3O4–CNTs nanocomposite, has been developed. It thus constitutes a very
simple, clean, economical and selective method for the aerobic preparation of benzils from
the corresponding benzoins. The catalyst can be re-used a number of times without losing
its catalytic activity to a greater extent.
Received 10 August 2013
Accepted after revision 5 September 2013
Available online xxx
Keywords:
ß 2013 Acade´mie des sciences. Published by Elsevier Masson SAS. All rights reserved.
Carbon nanotube
Nanocomposite
Benzil
Benzoin
Heterogeneous catalyst
Catalytic oxidation
1. Introduction
for the oxidation of benzoin limits their practical utiliza-
tions compared to heterogeneous catalysts in terms of
1,2-Diketones are very important structural moieties in
numerous biologically interesting compounds and are
broadly utilized for the construction of complex structures
in organic synthesis. Among the numerous 1,2-diketones,
benzil derivatives have received special attention, because
of their practical applications in organic and pharmaceu-
tical industry, such as photosensitive and synthetic
reagents [1]. Benzil is extensively used as a substrate in
product recovery, product selectivity, and environmental
concerns [6,7]. For the oxidation of benzoin to benzil using
a supported oxidant, such as ferric oxide–aluminium oxide
[8], VOCl3 [9], silica-supported manganese dioxide [10],
ammonium chlorochromate adsorbed on alumina [11] or
silica [12], and chromium trioxide on Kieselghur [13] were
exploited to overcome these difficulties. However, most of
these systems show relatively low selectivity toward the
desired products, or exhibit low activity. Therefore, the
desired product selectivity still remains a challenge for the
existing oxidation methods.
Carbon nanotubes (CNTs) with electrical, mechanical,
thermal, and optical properties, high surface-to-volume
ratio, structural flexibility, and chemical stability were
recently expected to be an advanced support for catalysts
[14]. More importantly, CNTs can also be used in composites
withmetallic oroxidenanoparticles toimprove thecatalytic
performance of these particles [14]. CNTs can not only
provide a support for anchoring well-dispersed nanoparti-
cles and work as a highly conductive matrix for enabling
benzylic rearrangements and also acts as
a starting
material for the synthesis of many heterocyclic com-
pounds [2,3], exhibiting biological activity, such as antic-
onvulsant derivative dilantin [4,5]. Oxidation of benzoin
into benzil is one of the most efficient and practical
methods in organic synthesis. In general, the oxidation of
benzoins has been accomplished using homogeneous and
heterogeneous catalysts. The use of homogeneous reagents
*
Corresponding author.
E-mail address: Safari@kashanu.ac.ir (J. Safari).
1631-0748/$ – see front matter ß 2013 Acade´mie des sciences. Published by Elsevier Masson SAS. All rights reserved.
http://dx.doi.org/10.1016/j.crci.2013.09.003
Please cite this article in press as: Safari J, et al. Co3O4-decorated carbon nanotubes as a novel efficient catalyst in the
selective oxidation of benzoins. C. R. Chimie (2014), http://dx.doi.org/10.1016/j.crci.2013.09.003

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J. Safari et al. / C. R. Chimie xxx (2014) xxx–xxx
good contact between them, but it can also effectively
prevent the volume expansion/contraction and aggregation
of nanoparticles during the catalytic process [15]. On the
other hand, among all metal oxides, an extreme interest has
been attached to Co3O4 because the carbon framework has a
large surface area for finely dispersing Co3O4 nanoparticles,
high electrical conductivity for providing electrical path-
ways, highly developed mesoporosity for facile diffusion of
electrolyte, and electrochemical stability for long-term
operation [16]. Co3O4 supported on CNTs are attracting
significant attention owing to their wide applications as
Schottky-junction diode [17], electrochemical capacitors
[18], Li-ion battery anode applications [19], and catalyst
[20]. To enhance the catalytic performance and high surface
area, Co3O4 can be used with carbon nanotubes (CNTs) to
form a composite material to be widely used as a catalyst
support [18].
In this report, we describe a convenient and efficient
selective oxidation of benzoin derivatives to the corre-
sponding benzils using Co3O4–CNT nanocomposites under
an air atmosphere. CNT and nanosized Co3O4 were
successfully composited to catalyze this oxidation process.
CNT serves to support the catalyst and provides a surface
for the oxidation reaction to occur. Co3O4–CNTs are
expected to show excellent catalytic activity owing to
their nanoscale size and large surface area. Therefore, we
would like to report, for the first time, the selective
oxidation of benzoins to benzils using Co3O4–CNT nano-
composites (Scheme 1).
microscopy (SEM) was performed on a FEI Quanta 200 SEM
operated at a 20-kV accelerating voltage. The samples for
SEM were prepared by spreading a small drop containing
nanoparticles onto a silicon wafer and dried almost
completely in the air at room temperature for 2 h, and
then transferred onto SEM conductive tapes.
2.2. Preparation of CNT–Co3O4 nanocomposites
CNT–Co3O4 nanocomposites were prepared according
to procedures reported in the literature [18]. In short, CNTs
were dissolved in a mixture of 98% sulphuric acid and 70%
nitric acid (volumetric ratio 3:1) at 50 8C under ultra-
sonication for 6 h. Then, MWCNTs were centrifuged and
washed with distilled water, then dried in an oven at
100 8C for 24 h. After that, 0.5 g of Co(NO3)2ꢀ6H2O was
dissolved into 40 mL of n-hexanol to form a red solution.
Seventy milligrams of acid-treated MWNTs were dispersed
in the red solution by sonication for 2 h. Then, this solution
was refluxed at 140 8C for 10 h. After cooling to ambient
temperature, the products were washed with cyclohexane
repeatedly to remove any impurities and dried. The black
powder was filtered and washed with ethanol and dried at
100 8C under a vacuum oven to obtain the CNT–Co3O4
composite as a catalyst.
2.3. General procedure for the oxidation of benzoins to benzils
To a mixture of benzoin (1 mmol) and CNT–Co3O4
catalyst (10 mol%) in a 100-mL flask, toluene (5 mL) was
added. The reaction mixture was stirred at 100 8C in the
atmospheric air. No device was used for pumping the air
into the reaction solution. The completion of the reaction
was monitored by TLC, visualized with ultraviolet light.
After complete disappearance of the benzoin, as monitored
by TLC (petroleum ether:ethyl acetate, 9:2), the reaction
mixture was filtered while the residue was washed with
hot toluene (2 ꢁ 5 mL) and water (3 ꢁ 15 mL). The product
was obtained after removal of the solvent under reduced
pressure, followed by crystallization. The catalyst was
recovered from the residue after washing with EtOH
(10 mL) followed by distilled water (200 mL) and then with
acetone (15 mL). It can be re-used after drying at 80 8C for
2 h. The structures of these compounds have been
investigated using different methods of spectrometry:
IR, 1H NMR, 13C NMR, CHN, and UV.
2. Experimental
2.1. Materials and instrumentation
Chemicals were purchased from Merck without any
further purification. IR spectra were recorded on KBr
pellets using a Perkin–Elmer 781 spectrophotometer and
an Impact 400 Nicolet FTIR spectrophotometer. 1H NMR
(400 MHz) and 13C NMR (100 MHz) spectra were recorded
with a Bruker DPX-400 Avance spectrometer. The melting
points were determined by a Yanagimoto micro melting
point apparatus. The purity determination of the sub-
strates and reaction monitoring were accomplished by thin
layer chromatography (TLC) on silica gel polygram SILG/
UV 254 plates. MWNTs were purchased from Nanotech
Port Co. (Taiwan). These MWNTs were produced via the
chemical vapour deposition (CVD, or sometimes called
catalytic pyrolysis) method. The outer diameter of CNTs
was between 20 and 40 nm. XRD patterns were acquired
on a Philips X’Pert, Netherlands, diffractometer equipped
3. Results and discussion
The oxidative functionalization of CNTs is important for
enhancing chemical activity and depositing metal oxide
´
˚
with a Cu K
a
radiation (
l
= 1.5406 A). Scanning electron
R2
R2
OH
O
CNT-Co3O4
100 oC, toluene, air
O
O
R1
R1
Scheme 1. Oxidation of benzoin to benzil derivatives using the Co3O4–CNT nanocomposite.
Please cite this article in press as: Safari J, et al. Co3O4-decorated carbon nanotubes as a novel efficient catalyst in the
selective oxidation of benzoins. C. R. Chimie (2014), http://dx.doi.org/10.1016/j.crci.2013.09.003

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3
Fig. 1. XRD patterns of (a) the CNT and (b) the CNT–Co3O4 nanocomposite.
nanoparticles as supports for heterogeneous catalysis
applications [21]. It is known that after oxidation with
sulphuric acid and nitric acid, the surface of MWNTs
possesses a great deal of functional carboxyl groups and
becomes negatively charged [18]. The positive cobalt ions
in the hydrophobic n-hexanol solution are adsorbed on the
surface of the acid-treated CNTs through electrostatic
attraction and then in situ decompose into Co3O4
according to the following process [18]:
SEM images, presented in Fig. 2, allow the non-
structural characterization of the CNT and Co3O4–carbon
nanotube nanocomposite samples. The average diameter
of carbon nanotubes was found to be 20 nm, as obvious
from Fig. 2a. The size distribution of Co3O4 nanoparticles
attached to the CNTs was found to be 48 nm of diameter,
which illustrates that it is larger than that of MWNT. SEM
images suggest that the Co3O4 nanoparticles are mostly
attached to the carbon nanotube. The weight ratio of the
CNT to the Co3O4 crystalline phase was 70:30, as
determined by inductively coupled plasma atomic emis-
sion spectroscopy analysis.
air; n
-
3CoðNO3Þ2
ꢂh!exanolCo3O4 # þ 6NO2 " þ O2 "
140ꢂ180ꢃC
After the characterization of the nanocatalyst, we
focused on the systematic evaluation of different catalysts
for examination of catalytic activity in aerobic oxidation of
benzoin to benzil. The fact that no conversion was obtained
carrying out a blank reaction (i.e. without catalyst) infers
that the catalyst is necessary for this transformation. In the
course of this study, CNT–Co3O4 was the most effective
catalyst (Table 1) with higher activity and better-con-
trolled selectivity because of a large specific surface area on
support of CNT.
The formation of the CNT–Co3O4 nanocomposite was
confirmed by X-ray diffraction (XRD); data are shown in
Fig. 1. The crystalline peaks can be clearly indexed as a
typical Co3O4 crystalline phase with a spinel structure
(JCPDS card No. 74–1666) in Fig. 1b. The XRD patterns of
the nanoparticles show six characteristic peaks, revealing a
cubic cobalt oxide phase (2u = 18.63, 26.22, 35.17, 43.55,
54.22, 60.08). These are related to their corresponding
indices (4 1 1), (3 1 1), (4 0 0), (3 3 1), and (4 2 2),
respectively. The broad peak located at approximately
To select the appropriate solvent, the reaction with test
substrates was carried out in different solvents. The results
2
u
= 26.28 is characteristic of a CNT (Fig. 1a and b, JCPDS
card No. 75–1621) [22].
Fig. 2. SEM images of the CNTs (a) and the Co3O4–MWCNT nanocomposites.
Please cite this article in press as: Safari J, et al. Co3O4-decorated carbon nanotubes as a novel efficient catalyst in the
selective oxidation of benzoins. C. R. Chimie (2014), http://dx.doi.org/10.1016/j.crci.2013.09.003

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Table 1
Table 3
The effect of the variations of different catalysts for the oxidation of
benzoin to benzil in liquid phase catalysisa.
The effect of variation of different oxidant for the oxidation of benzoin to
benzila.
Entry
Catalyst
Time (h)
Yield (%)b
Entry
Oxidants
Yield (%)b
1
2
3
4
5
No catalyst
MnO2
3
2
2
2
1
–
1
2
3
4
H2O2
30
50
20
95
30
20
45
65
m-perchlorobenzoic acid
TBHP
Al2O3
Co3O4
Air atmosphere
CNT–Co3O4
a
Reaction conditions: benzoin (1 mmol), catalyst (10 mol%), toluene
a
Reaction conditions: benzoin (1 mmol), catalyst (4 mol%), toluene
(5 mL), stirring at 100 8C
b
(5 mL), stirring at 100 8C under an air atmosphere.
Isolated yields (conversion of benzoin).
b
Isolated yields.
were summarized in Table 2. The results show that the
larger yield of benzil was achieved with toluene. When
other solvents were used, no significant improvement in
the yield was observed. It seems that in the oxidation
procedure, the non-occurrence of reaction in other
solvents may be due to the poor solubility of the products
in these solvents and the polarity of the latter. As shown in
Table 2, the best yield of product was achieved with the
catalyst ratio 10 mol% (Table 2, Entry 9).
This reaction is heterogeneous, taking place at the
Co3O4–CNT nanocomposite. On the other hand, the
nanocatalyst Co3O4 with high surface area on the CNT
can lead to higher performance of the catalyst compared to
the other catalysts. Moreover, the high efficiency of the
nanoparticle oxides not only is caused by their high surface
area but also it prevents agglomeration and therefore
enhances their performances. Whatever the amount of
catalyst, there is more oxygen adsorbed on the catalyst’s
surface, and the reaction is carried out efficiently.
more reactive and could be oxidized more easily (com-
pounds b and f). In contrast, the benzoins containing an
electron-withdrawing group have shown a lower reactiv-
ity (compound j). In this reaction, benzil was obtained as
the major product. Small amounts of C–C cleavage
products, benzaldehyde, and benzoic acid were also
detected.
After completion of the reaction, the catalyst was re-
used for the next cycle without any appreciable loss of its
activity. Similarly, reusability for sequential reaction was
also carried out and the catalyst was found to be reusable
for five cycles (Fig. 3).
4. Spectroscopic data
4.1. Compound (a), benzil
UV (CH3OH)
(ppm) 7.54 (t, 2H, CH, J = 7.6 Hz), 7.69 (t, 4H, CH, J = 7.6 Hz),
7.98 (d, 4H, CH, J = 7.6 Hz); 13C NMR (CDCl3, 100 MHz)
l d
max: 224 nm; 1H NMR (CDCl3, 400 MHz)
Among the various oxidants (H2O2, m-perchlorobenzoic
acid, and air), it was concluded that the best activity and
selectivity could be achieved by air itself under optimized
reaction conditions (Table 3). Moreover, it was found that
the air present inside the reaction mixture itself is enough
to derive this reaction.
d
(ppm) 128.90 (4CH), 129.70 (4CH), 133 (2CH), 134.93 (2C),
194.30 (2CO); IR (KBr) cmꢂ1 1650 (C5O, s), 1450, 1580
(C5C, m), 720 (CH, m); Anal. calcd. (%) C, 79.99; H, 4.79; O,
15.22; found C, 79.91; H, 4.73; O, 15.12.
As shown in Table 4, in this reaction, the oxidation of
benzoins by CNT–Co3O4 was carried out in good yield.
From the results in Table 4, it seems that the benzoins
containing an electron-donating group were found to be
4.2. Compound (b), 4,40-dimethoxybenzil
UV (CH3OH)
(ppm) 3.89 (s, 6H, OCH3), 6.97 (d, 4H, CH, J = 8.8 Hz), 7.95
(d, 4H, CH, J = 8.8 Hz); 13C NMR (CDCl3, 100 MHz)
(ppm)
l d
max: 225 nm; 1H NMR (CDCl3, 400 MHz)
d
55.62 (2OCH3), 114.29 (4CH), 126.19 (4CH), 132.30 (2C),
64.86 (2C), 193.54 (2CO); IR (KBr) cmꢂ1 1650 (C5O, s),
1586 (C5C, m), 769 (CH, m); Anal. calcd. (%): C, 71.10; H,
5.22; O, 23.68; found: C, 70.98; H, 5.19; O, 23.64.
Table 2
The effect of amount of catalyst and solvent on the yield of the oxidation
of benzoina.
Entry
Nanocatalyst
(mol%)
Solvent
Time (h)
Yield (%)b
4.3. Compound (c), 4-dimethylaminobenzil
1
2
3
4
5
6
7
8
9
10
4
Toluene
CCl4
1
3
3
5
5
5
1
1
1
1
65
45
40
–
4
UV (CH3OH) l d
max: 229 nm; 1H NMR (CDCl3, 400 MHz)
(ppm) 3.38 (s, 6H, CH3), 6.67 (d, 2H, CH, J = 5.2 Hz), 7.48 (d,
2H, CH, J = 8.1 Hz), 7.61 (d, 2H, CH, J = 8.1 Hz), 7.8 (d, H, CH,
J = 8.1 Hz), 8.28 (d, 2H, CH, J = 5.2 Hz); 13C NMR (CDCl3,
4
CH2Cl2
CH3OH
EtOH
4
4
–
4
H2O
–
6
Toluene
Toluene
Toluene
Toluene
75
85
95c
95
100 MHz)
d (ppm) 55.91 (2CH3), 111.20 (2CH), 128.90
8
(2CH), 129.01 (C), 129.70 (2CH), 135.37 (CH), 135.50 (C),
141.47 (C), 153.76 (C), 196.72 (CO); IR (KBr) cmꢂ1 1650,
1700 (C5O, s), 1440, 1620 (C5C, m), 705 (CH, m); Anal.
calcd. (%) C, 75.87; H, 5.97; N, 5.53; O, 12.63; found C,
75.82; H, 5.95; N, 5.50; O, 12.61.
10
12
a
Reaction conditions: benzoin (1 mmol), solvent (5 mL), stirring at
100 8C under air atmosphere.
b
Isolated yields (Conversion of benzoin).
c
The best yield of product.
Please cite this article in press as: Safari J, et al. Co3O4-decorated carbon nanotubes as a novel efficient catalyst in the
selective oxidation of benzoins. C. R. Chimie (2014), http://dx.doi.org/10.1016/j.crci.2013.09.003

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Table 4
Selective oxidation of benzoins in the presence of CNT–Co3O4 under an air atmospherea.
Entry
R1
R2
Product
Time
(h)
Conversion of benzoin
(%)
Selectivity of benzil
(%)
mprep/mplit. (8C)
1
2
3
4
5
6
7
8
9
10
H
H
a
b
c
d
e
f
1
95
92
70
85
91
93
85
67
88
60
85
78
60
65
75
80
68
50
70
40
93–95/94–96 [23]
133–135/132–134 [23]
116–118/115–116 [23]
102–104/101–104 [23]
65–67/62–63 [23]
119–121
4-OCH3
4-NCH3
4-CH3
4-OCH3
NC5H5
2,4-diOCH3
H
4-OCH3
H
0.90
1.20
0.60
0.90
0.85
1.25
0.90
1
4-CH3
H
NC5H5
2,4-diOCH3
3-OCH3
4-CH3
3-Br
g
h
i
195–197
133–134/133 [23]
27–29/31 [23]
H
4-CH3
j
1.20
141–142
a
Reaction conditions: benzoin (1 mmol), catalyst (10 mol%), toluene (5 mL), and 100 8C was the reaction temperature.
(2CH), 137.26 (2CH), 149.46 (2CH), 151.65 (2C), 197.02
(2CO); IR (KBr) cmꢂ1 1713 (C5O, s), 1274 (C5N, s), 1505
(C5C, m); Anal. calcd. (%) C, 67.92; H, 3.80; N, 13.20; O,
15.08; found C, 67.90; H, 3.78; N, 13.10; O, 15.04.
4.7. Compound (g), 2,20,4,40-tetramethoxybenzil
UV (CH3OH) l d
max: 226 nm; 1H NMR (CDCl3, 400 MHz)
(ppm) 3.88 (s, 3H, OCH3), 3.90 (s, 3H, OCH3), 6.44 (s, 2H,
CH), 6.53 (d, 2H, CH, J = 8.4 Hz), 7.81 (d, 2H, CH, J = 8.8 Hz);
13C NMR (CDCl3, 100 MHz)
d (ppm) 55.23 (OCH3), 55.80
(OCH3), 101.58 (2CH), 113.03 (2CH), 116.91 (2C), 131.22
(2CH), 161.83 (2C), 162.93 (2C), 186.91 (2CO); IR (KBr)
cmꢂ1 1630–1680 (C5O, s), 1470, 1618 (C5C, m), 738 (CH,
m); Anal. calcd. (%) C, 65.45; H, 5.49; O, 29.06; found C,
65.41; H, 5.43; O, 29.01.
Fig. 3. Recyclability of CNT–Co3O4 in the reaction of benzoin (1 mmol),
catalyst (10 mol%), toluene (5 mL), under stirring at 100 8C in the air.
4.8. Compound (h), 3-methoxybenzil
4.4. Compound (d), 4,40-dimethylbenzil
UV (CH3OH) l d
max: 234 nm; 1H NMR (CDCl3, 400 MHz)
(ppm) 3.72 (s, 3H, OCH3), 7.01 (1H, t), 7.1 (1H, s) 7.32 (1H,
d), 751 (2H, t), 7.60 (1H, t), 7.72 (2H, d); 13C NMR (CDCl3,
UV (CH3OH)
(ppm) 2.45 (s, 6H, CH3), 7.4 (d, 4H, CH, J = 7.2 Hz), 7.75 (d,
4H, CH, J = 7.6 Hz); 13C NMR (CDCl3, 100 MHz)
(ppm)
l
max: 225 nm; 1H NMR (CDCl3, 400 MHz)
d
d
100 MHz) d (ppm) 54.00 (OCH3), 116.80 (CH), 120.13 (CH),
21.95 (2CH3), 129.72 (4CH), 130.03 (4CH), 130.69 (2C),
146.11 (2C), 194.54 (2CO); IR (KBr) cmꢂ11650, (C5O, s),
1586 (C5C, m), 769 (CH, m); Anal. calcd. (%) C, 80.65; H,
5.92; O, 13.43; found C, 80.63; H, 5.90; O, 13.40.
124.16 (CH), 128.90 (2CH), 129.70 (2CH), 131.05 (CH),
131.37 (CH), 132.88 (C), 135.27 (C), 163.09 (C), 193.41
(CO), 194.30 (CO); IR (KBr) cmꢂ11660, (C5O, s), 1396, 1613
(C5C, m), 725 (CH, m); Anal. calcd. (%): C, 74.99; H, 5.03; O,
19.98; found C, 74.95; H, 4.98; O, 19.94.
4.5. Compound (e), 4-methoxybenzil
4.9. Compound (i), 4-methylbenzil
UV (CH3OH)
(ppm) 3.76 (s, 3H, OCH3), 6.82 (2H, d), 7.34–7.61 (5H, m)
7.86 (2H, d); 13C NMR (CDCl3, 100 MHz)
(ppm) 55.19
l d
max: 228 nm; 1H NMR (CDCl3, 400 MHz)
UV (CH3OH) l d
max: 223 nm; 1H NMR (CDCl3, 400 MHz)
(ppm) 2.34 (s, 3H, CH3), 7.3 (m, 2H), 7.35 (m, 2H), 7.42 (t,
d
(CH3), 113.20 (2CH), 128.90 (2CH), 129.70 (2CH), 130.30
(C), 131.37 (CH), 133 (2CH), 133.26 (C), 164.69 (C), 194.30
(CO); IR (KBr) cmꢂ1 1650, (C5O, s), 1586 (C5C, m), 769
(CH, m); Anal. calcd. (%) C, 74.99; H, 5.03; O, 19.98; found C,
74.91; H, 4.98; O, 19.96.
1H, J = 8 Hz), 7.55 (t, 2H, J = 8, 7.2 Hz), 7.92 (d.d, 2H, J = 7.92,
1.2 Hz); 13C NMR (CDCl3, 100 MHz)
d (ppm) 22.06 (CH3),
122.71 (2CH), 130.12 (2CH), 130.28 (2CH), 131.18 (2CH),
132.54 (2CH), 133.17 (C), 133.83 (C), 147.02 (C), 193.95
(CO), 194.08 (CO); IR (KBr) cmꢂ11640, 1680, (C5O, s), 1420,
1630 (C5C, m), 724 (CH, m); Anal. calcd. (%) C, 80.34; H,
5.39; O, 14.27; found C, 80.32; H, 5.35; O, 14.24.
4.6. Compound (f), 2-pyridil
UV (CH3OH)
l
max: 365 nm; 1H NMR (CDCl3, 400 MHz)
d
4.10. Compound (j), 3-Bromo-40-methylbenzil
(ppm) 7.49 (t, 2H, CH, J = 8.1 Hz), 7.91 (t, 2H, CH, J = 8.1 Hz),
8.18 (d, 2H, CH, J = 8.1 Hz), 8.56 (d, 2H, CH, J = 8.1 Hz); 13C
UV (CH3OH)
d (ppm) 2.42 (s, 3H, CH3), 7.34 (t, 1H, CH), 7.61 (d, 1H,
l
max: 227 nm; 1H NMR (CDCl3, 400 MHz)
NMR (CDCl3, 100 MHz)
d
(ppm) 122.27 (2CH), 127.99
Please cite this article in press as: Safari J, et al. Co3O4-decorated carbon nanotubes as a novel efficient catalyst in the
selective oxidation of benzoins. C. R. Chimie (2014), http://dx.doi.org/10.1016/j.crci.2013.09.003

G Model
CRAS2C-3818; No. of Pages 6
6
J. Safari et al. / C. R. Chimie xxx (2014) xxx–xxx
References
CH), 7.74 (d, 3H, 3CH), 8.04 (s, H, CH), 8.59 (s, 1H, CH),
8.65 (s, 1H, CH); 13C NMR (CDCl3, 100 MHz)
(ppm)
d
[1] (a) K.H. Kim, B.R. Park, J.W. Lim, J.N. Kim, Tetrahedron Lett. 52 (2011)
3463–3466;
55.65 (CH3), 144.44 (2CH), 123.21 (C), 129.12 (CH),
129.76 (C), 130.47 (2CH), 131.37 (CH), 132.44 (CH),
134.91 (CH), 137.46 (C), 165.18 (C), 192.04 (CO), 193.08
(CO); IR (KBr) cmꢂ1 1640, 1700, (C5O, s), 1420, 1620
(C5C, m), 705, 730 (CH, m); Anal. calcd. (%) C, 56.45;
H, 3.47; Br, 25.04; O, 15.04; found C, 56.43; H, 3.44;
Br, 25.01; O, 15.01.
(b) K. Skobridis, V. Theodorou, E. Weber, ARKIVOC (2006) 102–106.
[2] H. Wynberg, H.J. Kooreman, J. Am. Chem. Soc. 87 (1965) 1739–1742.
[3] W.W. Paudler, J.M. Barton, J. Org. Chem. 31 (1966) 1720–1722.
[4] W.R. Dunnavant, F.L. James, J. Am. Chem. Soc. 78 (1956) 2740–2743.
[5] D. Sachdev, M.A. Naik, A. Dubey, B.G. Mishra, Catal. Commun. 11 (2010)
684–688.
[6] S.M.I. Morsy, S.A. Shaban, A.M. Ibrahim, M.M. Selim, J. Alloy Compd. 486
(2009) 83–87.
[7] W.Y. Sun, N. Ueyama, A. Nakamura, Tetrahedron 48 (1992) 1557–1566.
[8] Y. Jiang, Y. Wu, B. Xie, Y. Qian, Mater. Chem. Phys. 74 (2002) 234–237.
[9] R. Garavaglia, C.M. Mari, S. Trasatti, Surf. Technol. 19 (1983) 197–215.
[10] G. Furlanetto, L. Formaro, J. Colloid Interface Sci. 170 (1995) 169–175.
[11] M.F. Irfan, J.H. Goo, S.D. Kim, Appl. Catal., B: Environ. 78 (2008) 267–274.
[12] Q. Yan, X. Li, Q. Zhao, G. Chen, J. Hazard. Mater. 209–210 (2012) 385–391.
[13] J.D. Lou, C. Zhang, G.Q. Wang, C. Gao, Synth. React. Inorg. Met.-Org.,
Nano-Met. Chem. 39 (2008) 6–8.
[14] (a) J. Safari, S. Gandomi-Ravandi,J.Mol.Catal. A:Chem. 373 (2013) 72–77;
(b) J. Safari, S. Gandomi-Ravandi, J. Mol. Catal. A: Chem. 371 (2013)
135–140.
[15] X.M. Liu, Z.D. Huang, S.W. Oh, B. Zhang, P.C. Ma, M.M.F. Yuen, J.K. Kim,
Compos. Sci. Technol. 72 (2012) 121–144.
5. Conclusions
In conclusion, the oxidation of benzoin was carried out
using the CNT–Co3O4 composite under milder reaction
conditions. CNT–Co3O4 is an effective catalyst in the
oxidation of benzoin to benzil. Very high activity and
selectivity of the product were obtained. Moreover, the
mild reaction conditions, high yield of products, ease of
work-up, and the selective procedure will make the
present method a useful and important addition to the
present methodologies for the oxidation of benzoins to the
corresponding benzils.
[16] J. Parka, W.G. Moon, G.P. Kim, I. Nam, S. Park, Y. Kimb, J. Yi, Electrochim.
Acta 105 (2013) 110–114.
[17] L. Fu, Z. Liu, Y. Liu, B. Han, P. Hu, L. Cao, D. Zhu, Adv. Mater. 17 (2005)
217–221.
[18] Y. Shan, L. Gao, Mater. Chem. Phys. 103 (2007) 206–210.
[19] S.M. Abbas, S.T. Hussain, S. Ali, N. Ahmad, N. Ali, K.S. Munawar,
Electrochim. Acta 105 (2013) 481–488.
Acknowledgement
[20] S. Jiang, S. Song, Appl. Catal. B: Environ. 140–141 (2013) 1–8.
[21] M. Tre´panier, A. Tavasoli, A.K. Dalai, N. Abatzoglou, Fuel Process Tech-
nol. 90 (2009) 367–374.
[22] T.H. Yoon, Y.J. Park, Nanoscale Res. Lett. 7 (2012) 1–4.
[23] M. Balalaie, M.S. Golizeh, Hashtroudi, Green Chem. 2 (2000) 277–278.
We gratefully acknowledge the financial support from
the Research Council of the University of Kashan for
supporting this work by Grant No. 256722/V.
Please cite this article in press as: Safari J, et al. Co3O4-decorated carbon nanotubes as a novel efficient catalyst in the
selective oxidation of benzoins. C. R. Chimie (2014), http://dx.doi.org/10.1016/j.crci.2013.09.003