β-cyclodextrin polymer promoted green synthesis of cinnamaldehyde to natural benzaldehyde in aqueous solution

Article abstract of DOI:10.1080/10610278.2012.688119

An environmentally benign synthesis of natural benzaldehyde from cinnamaldehyde under mild conditions has been investigated with sodium hypochlorite as oxidant and β-cyclodextrin polymer as phase-transfer catalyst. The polymer showed excellent catalytic a

Full text of DOI:10.1080/10610278.2012.688119

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β-Cyclodextrin polymer promoted green synthesis of
cinnamaldehyde to natural benzaldehyde in aqueous
solution
a
b
a
b
a
Zu-Jin Yang , Hong-Guo Jiang , Xian-Tai Zhou , Yan-Xiong Fang & Hong-Bing Ji
a
School of Chemistry and Chemical Engineering, Sun Yat-sen University , Guangzhou ,
10275 , P.R. China
5
b
Faculty of Chemical Engineering and Light Industry, Guangdong University of Technology ,
Guangzhou , 510006 , P.R. China
Published online: 07 Jun 2012.
To cite this article: Zu-Jin Yang , Hong-Guo Jiang , Xian-Tai Zhou , Yan-Xiong Fang & Hong-Bing Ji (2012) β-Cyclodextrin
polymer promoted green synthesis of cinnamaldehyde to natural benzaldehyde in aqueous solution, Supramolecular
Chemistry, 24:6, 379-384, DOI: 10.1080/10610278.2012.688119
To link to this article: http://dx.doi.org/10.1080/10610278.2012.688119
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Supramolecular Chemistry
Vol. 24, No. 6, June 2012, 379–384
b-Cyclodextrin polymer promoted green synthesis of cinnamaldehyde to natural benzaldehyde
in aqueous solution
a
Zu-Jin Yang , Hong-Guo Jiang , Xian-Tai Zhou , Yan-Xiong Fang and Hong-Bing Ji *
b
a
b
a
a b
School of Chemistry and Chemical Engineering, Sun Yat-sen University, Guangzhou 510275, P.R. China; Faculty of Chemical
Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, P.R. China
(
Received 17 December 2011; final version received 20 April 2012)
An environmentally benign synthesis of natural benzaldehyde from cinnamaldehyde under mild conditions has been
investigated with sodium hypochlorite as oxidant and b-cyclodextrin polymer as phase-transfer catalyst. The polymer
showed excellent catalytic activity exhibiting 92% conversion and 62% selectivity to benzaldehyde at ambient pressure and
at 708C. This catalyst could be recovered and reused six times, and the catalyst efficiency remained unchanged, which
suggests that the catalyst is an efficient and green catalyst for oxidation of cinnamaldehyde. The results reported herein may
be a promising method in industry for the synthesis of natural benzaldehyde.
Keywords: phase-transfer catalyst; benzaldehyde; sodium hypochlorite; b-cyclodextrin polymer; mechanism
1
.
Introduction
by glycosidic bonds. They are water soluble, non-toxic
and hydrophobic in the central cavity. The most significant
characteristic of the CDs is the ability to form inclusion
complexes with different guest molecules in aqueous
solution or in the solid state through host–guest
interactions (15–17). b-CD is the cheapest among
the CD family and has been widely used in separation,
catalysis, and in organic reactions (18–21). And it has
played a vital role in activating substrate and improving its
selectivity (22–24). Although b-CD exhibits good
catalytic activity in liquid-phase oxidation, the separation
of b-CD from the homogeneous system is very difficult.
Therefore, b-CD was immobilised on appropriate supports,
e.g. organic, polymeric and mineral materials due
to its recyclability, easy recovery and cost-effectiveness
Benzaldehyde is the second most utilised flavour
compound in the world, and it is widely used in cosmetics,
perfumery, food and pharmaceutical industries (1–3).
With more care about food quality, consumers prefer
natural products, and the demand for natural benzaldehyde
is increasing rapidly. Because of the limited supply and
high price of the natural product, synthetic benzaldehyde
produced from natural cinnamon oil, which contains more
than 80% of cinnamaldehyde, under mild conditions is
often used as an alternative (4). Conventionally, preparing
natural benzaldehyde is mostly from alkaline of Laetrile.
However, toxic hydrocyanic acid is produced, which must
be removed thoroughly from benzaldehyde and the rest of
the oil prior to use. In this way, the natural benzaldehyde
could be obtained at high cost.
(
25). Immobilised b-CD not only shows mechanical
properties but also completely retains molecular recog-
nition and catalytic properties of cyclodextrins. One way
for producing immobilised b-CD (abbreviated as b-CDP)
is through the reaction of b-CD molecules with
bifunctional crosslinking agents such as epichlorohydrin
Other techniques for producing natural benzaldehyde
from alkaline hydrolysis of cinnamaldehyde or natural
cinnamon oil (5–7) are known. However, these techniques
produce natural benzaldehyde in a low yield because
cinnamon oil or cinnamaldehyde are poorly soluble in
water, making the resulting process less economical.
In order to promote the reaction in aqueous solution, phase
transfer or surfactants (8–10) have been utilised to increase
the contact between the two phases. However, there are also
some drawbacks, e.g. many by-products and toxic phase-
transfer catalysts remained. Cyclodextrins (CDs) have been
introduced into many organic reactions in aqueous solution
(EPI) (26).
Sodium hypochloride is an effective, inexpensive and
non-toxic oxidant, which has been reported in the liquid-
phase oxidation (27, 28). In this work, the catalytic
oxidation of cinnamaldehyde to natural benzaldehyde
using b-CDP as a phase-transfer catalyst and sodium
hypochloride as an oxidant has been investigated for the
first time (Scheme 1). This methodology might provide
promising opportunity for industrial applications in the
field of natural benzaldehyde.
(
11–14). CDs are cyclic oligosaccharides composed of
–8 glucopiranose units (namely a-, b- and g-CDs) linked
6
*Corresponding author. Email: jihb@mail.sysu.edu.cn
ISSN 1061-0278 print/ISSN 1029-0478 online
q 2012 Taylor & Francis
http://dx.doi.org/10.1080/10610278.2012.688119
http://www.tandfonline.com

3
80
Z.-J. Yang et al.
β-CDP
100
O
O
NaOCl, H O, 343K
90
80
2
Scheme 1. Oxidation of cinnamaldehyde to benzaldehyde
catalysed by b-CDP.
7
6
5
4
0
0
0
0
2
.
Results and discussions
2.1 Fourier transform infrared spectroscopy (FTIR)
characterisation
FTIR spectra of b-CD (a) and b-CDP (b) are shown in
Figure 1. FTIR spectrum of b-CDP is similar to that of b-
CD, indicating that the frame of b-CD does not change.
The peaks of b-CDP at 3446 and 2876 cm are stronger
than those of b-CD, and the increased intensity may be
attributed to the presence of more ZOH and ZCH groups
1
00
200
300
400
500
600
2
1
Stirring speed (rpm)
Figure 2. Stirring speed on the oxidation of cinnamaldehyde.
Reaction conditions: cinnamaldehyde (1 mmol), b-CDP (1 g),
2
NaClO [4 ml, 7.5% (w/w)], H O (25 ml), 708C and 2 h.
2
in the b-CDP. The spectrum of b-CDP showed the
2
characteristic peak at 1260 and 720 cm , indicating the
1
formation of the expoxy group onto b-CDP. The peak at
2
030 cm in the b-CDP was assigned to the CZO or
1
in stirring speed. When the speed is 400 rpm, the
conversion is up to 92%, which was much higher than
1
CZOZC stretching in the b-CDP. The increase in the
2
band intensity at around 1030 cm might be b-CD. In
1
50.5% at the stirring speed of 100 rpm. Furthermore, there
2
1
is no significant influence on the conversion of
cinnamaldehyde with an increase in the stirring speed
beyond 400 rpm. The results indicated that the conversion
of cinnamaldehyde was strongly dependent on the
dispersed extent of organic phase in aqueous phase,
which promoted the mass transfer between the two phases
to improve the selectivity of natural benzaldehyde. The
optimal stirring speed is 400 rpm. Siva and Murugan (30)
reported similar behaviour displayed by reactions with a
real ‘phase transfer’.
addition, the peak at 890 cm in the b-CDP was the
characteristic bands of a-(1,4)-glucopyranose in b-CD
(29). Therefore, it could be concluded that b-CD had been
immobilised successfully onto b-CDP.
2
.2 Effect of stirring speed
Stirring speed has a great influence on the oxidation of
cinnamaldehyde by b-CDP catalysis. The effect of stirring
speed was investigated in the range of 100–600 rpm in
Figure 2. The results showed the conversion of
cinnamaldehyde significantly increased with increasing
2.3 Effect of amount of catalyst
The effect of amount of b-CDP on the yield of natural
benzaldehyde and the conversion of cinnamaldehyde was
investigated by varying its amount from 1 to 5 g. As shown
in Figure 3, b-CDP exhibited higher catalytic activity for
the oxidation of cinnamaldehyde to natural benzaldehyde
comparing with that in blank experiment, in which only
8
90
(a)
3
420
2876
1
030
1
260
7
20
51% cinnamaldehyde could be converted. The conversion
of cinnamaldehyde increased with the amount of catalyst,
which should be attributed to the increase in the number of
hydrophobic cavity in b-CDP. As reported by Ji et al. (31),
it is well known that b-CDP and substrate can form host–
guest inclusion complex, resulting in enhancing the
solubility of cinnamaldehyde in water and promoting the
reaction of cinnamaldehyde compared with experimental
result blank. Maximal conversion (ca. 92%) was obtained
when using 1.0 g of b-CDP. The excess amount of the
catalyst caused decrease of selectivity to benzaldehyde. It
could be attributed to further oxidation of benzaldehyde to
benzoic acid. The optimal amount of b-CDP is 1.0 g.
(
b)
4
000
3500
3000
2500
Wavenumber/cm–1
2000
1500
1000
500
Figure 1. FTIR spectra of b-CD (a) and b-CDP (b).

Supramolecular Chemistry
381
temperature was beyond 708C due to the undesirable side
reaction. As shown in Figure 4, the optimal reaction
temperature for oxidation of cinnamaldehyde is 708C.
1
00
70
9
8
7
6
5
0
0
0
0
0
6
5
4
3
0
0
0
0
2.5 Effect of molar ratio of NaClO to cinnamaldehyde
The amount of NaClO used in the system is another
important factor influencing the oxidation of cinnamalde-
hyde. The effect of NaClO/cinnamaldehyde molar radio
on the oxidation of cinnamaldehyde to benzaldehyde was
studied, and the results are shown in Table 1. The
conversion increased with increasing the molar ratio of
NaClO/cinnamaldehyde. About 92% conversion of
cinnamaldehyde and 62% selectivity of benzaldehyde
were obtained when the molar ratio of NaClO/cinnamal-
dehyde reached 4:1. When the ratio was increased,
cinnamaldehyde was completely converted. However, the
selectivity for benzaldehyde decreased when the ratio was
above 4:1. It could be attributed to that benzaldehyde was
further oxidised to benzoic acid at higher molar ratio of
NaClO/cinnamaldehyde. As shown in Table 1, optimal
ratio of NaClO/cinnamaldehyde was 4:1.
Conversion
Selectivity
0
1
2
3
4
5
Amount of catalyst (g)
Figure 3. Amount of catalyst on the oxidation of
cinnamaldehyde. Reaction conditions: cinnamaldehyde
(1 mmol), NaClO [4 ml, 7.5% (w/w)], H O (25 ml), 708C, 2 h
2
and 400 rpm.
2
.4 Effect of reaction temperature
The effect of reaction temperature on the oxidation of
cinnamaldehyde to benzaldehyde by b-CDP was investi-
gated under the temperature range of 30–808C with other
parameters being kept constant, and the results are shown
in Figure 4.
2.6 Large-scale experiment
As shown in Figure 4, the conversion of cinnamalde-
hyde increased with increasing the reaction temperature
from 30 to 808C. Nearly, 100% conversion of cinnamal-
dehyde was achieved at 808C. It seems that the selectivity
for benzaldehyde was closely related to the reaction
temperature. The selectivity for benzaldehyde increased
from 32% to 62% with rising temperature from 30 to 708C.
The selectivity for benzaldehyde decreased when the
Furthermore, in order to verify the efficiency of the
catalytic system, a large-scale experiment for oxidation of
cinnamaldehyde to benzaldehyde catalysed by b-CDP in
the presence of NaClO in water under the above optimum
reaction conditions was carried out as shown in Scheme 2.
The isolated yield of benzaldehyde was 57%. Comparing
with other ways of preparing benzaldehyde from
cinnamaldehyde (22), this process realised the clean
1
00
6
5
4
0
0
0
8
6
4
2
0
0
0
0
Conversion
Selectivity
30
20
3
0
40
50
60
70
80
Temperature/°C
Figure 4. Temperature on the oxidation of cinnamaldehyde. Reaction conditions: cinnamaldehyde (1 mmol), b-CDP (1 g), NaClO
4 ml, 7.5% (w/w)], H O (25 ml), 2 h and 400 rpm.
[
2

3
82
Z.-J. Yang et al.
Table 1. Effect of molar ratio of NaClO to cinnamaldehyde on
the oxidation of cinnamaldehyde.
1
00
a
NaClO:cinnamaldehyde
(mol:mol)
Conversion
(%)
Selectivity
(%)
8
6
4
0
0
0
Entry
1
2
3
4
5
0.5:1
1:1
2:1
3:1
4:1
31
48
60
74
92
50
52
54
59
61
a
b
c
d
e
a
Reaction conditions: cinnamaldehyde (1 mmol), b-CDP (1 g), H
25 ml), 708C, 2 h and 400 rpm.
2
O
20
0
(
O
0
40
80
120
160
200
β-CDP(10g)
O
Time (min)
NaClO (4mmol), H O, 343K, 2h
2
1
0 mmol
Isolated yield:57%
Figure 5. Plots of conversions and yields of the products versus
reaction time for the cinnamaldehyde/b-CDP/NaClO oxide
system at 708C: (a) conversion of cinnamaldehyde; (b) yield of
benzaldehyde; (c) yield of epoxide; (d) yield of
phenylacetaldehyde and (e) yield of benzoic acid.
Scheme 2. Large-scale oxidation of cinnamaldehyde to
benzaldehyde catalysed by b-CDP in the presence of NaClO.
synthesis of natural benzaldehyde and provided middle
yield for natural benzaldehyde under mild conditions
which is very important to preserve natural essence of
benzaldehyde during the reaction process.
intermolecular hydrogen bonding OZH· · ·O at the second
rim of b-CD. Small amount of the complex can directly
react with NaClO to produce benzaldehyde. Secondly, the
non-covalent intermolecular interaction between b-CD
and cinnamaldehyde also promotes the nucleophilic
oxidation. Larger amount of cinnamaldehyde is converted
into two intermediates including epoxide and phenylace-
taldehyde. Thirdly, the corresponding intermediates are
further oxidised to benzaldehyde by hypochlorite ion.
Finally, a small amount of benzaldehyde produced slowly
diffuses into bulk of aqueous solution and is further
oxidised into benzoic acid.
2.7 Plausible mechanism for oxidation
of cinnamaldehyde to benzaldehyde
The progress of the oxidation of cinnamaldehyde to
benzaldehyde catalysed by b-CDP in the presence of
NaClO in a batch was carried out by measuring reaction
samples using GC-MS with naphthalene as an internal
standard. The plots of the conversion of cinnamaldehyde
and the yields of the products versus reaction time were
shown in Figure 5. The conversion of cinnamaldehyde was
greatly increased by the addition of NaClO with extending
the reaction time, and 92% conversion was obtained at the
time of 30 min. And the yield of benzaldehyde reached
2.8 Reusability of the catalyst
The insoluble b-CDP could be easily recycled by
centrifugation after the reaction. The filtered b-CDP was
washed with ethanol and deionised water. After drying, the
catalyst was reused for the next run under the same
condition. As shown in Figure 7, the results indicated that
the catalytic activity was not affected significantly. Similar
conversion and selectivity were obtained when the
recovered b-CDP was reused six times.
5
7% at the time of 120 min and decreased a little due to
further oxidation to benzoic acid beyond 120 min.
However, the yield of epoxide almost simultaneously
reached up to 40% at the time of 15 min and then gradually
decreased to 8%. At the same time, the yield of
phenylacetaldehyde gradually increased to 12% and
decreased to 9% at the time of 180 min. According to
the previous reports (27, 28), sodium hypochloride is an
effective, inexpensive and non-toxic oxidant. It can
efficiently promote epoxide and phenylacetaldehyde to
benzaldehyde in the system. The above results suggest that
epoxide and phenylacetaldehyde are intermediates in the
reaction. Therefore, the mechanism has been proposed for
b-CDP-catalysed oxidation of cinnamaldehyde by sodium
hypochloride based on above experimental results, as
shown in Figure 6. Firstly, b-CD in the b-CDP and
cinnamaldehyde can form the inclusion complex via
3.
Conclusions
In conclusion, natural benzaldehyde has been successfully
obtained using b-CDP as phase-transfer catalyst in
aqueous solution. The b-CDP catalyst is found to be
recyclable and efficient for selective oxidation of
cinnamaldehyde to natural benzaldehyde with sodium
hypochloride as an oxidant, and 92% cinnamaldehyde
conversion and 57% benzaldehyde selectivity could be

Supramolecular Chemistry
383
H
ClO–
O
ClO–
H
O
ClO–
O
O
Cl– OH–
H
Cl–
O
O
O
O
O
OH–
O
O
O
HO
HO
O
O
HO
HO
O
Cl–
OH
HO
Cl–
O
O
O
OH
OH
O
OH
OH
O
O
O
O
ClO–
O
HO
HO
HO
ClO–
O
Cl–
O
HO
O
O
Cl–
HO
O
O
ClO–
OH
Figure 6. The mechanism of the oxidation of cinnamaldehyde and the by-product formed.
obtained within 2 h. This method is bestowed with merits
such as high yield, cost-effectiveness, biomimetic, neutral
aqueous-phase conditions and environmentally benign
nature. These are beneficial for keeping the natural essence
of natural benzaldehyde. Furthermore, the solid b-CDP
can be conveniently used in continuous operation. These
advantages of the catalyst made it referential for the
synthesis of natural benzaldehyde in industrial process.
4.
Experimental
4.1 Chemicals
b-CD was obtained from Shanghai Boao Biotechnology
(Shanghai, China). EPI was supplied from Tianjin Damao
Chemical Reagent Factory (Tianjin, China). Cinnamalde-
hyde (.99%) was obtained from Sinopharmacy Chemical
Reagent(Shanghai, China). Otherchemicalswerepurchased
from Guangzhou Chemical Reagent Factory (Guangzhou,
China). All reagents and solvents were of analytical grade
and used without further purification unless indicated.
Conversion
Selectivity
1
00
8
6
4
2
0
0
0
0
0
4.2 Catalyst preparation
According to the previous report (32), a typical procedure
for preparing b-CDP was described as follows: b-CD (5 g,
0.44 mmol) was mixed with 8 ml NaOH (50%, w/w)
solution and mechanically stirred for 20 min till b-CD was
dissolved completely. Then, 15 ml EPI was slowly added
into the mixture. The reaction mixture was heated to 658C
and kept at the same temperatureduring polymerisation.
After stirring (200 rpm) for about 2 h, the insoluble
Fresh First Scecond Third Fourth Fifth Sixth
Figure 7. Catalyst (b-CDP) recyclability data. Reaction
conditions: cinnamaldehyde (1 mmol), b-CDP (1 g), H
25 ml), NaClO [4 ml, 7.5% (w/w)], 608C, 2 h and 400 rpm.
2
O
(

3
84
Z.-J. Yang et al.
polymers were poured into water and washed until it
becomes neutral. The resulting product was filtrated and
further washed with acetone in a Soxhlet extractor for 24 h.
After drying in vacuum at 608C for 12 h, the product was
crushed and granulated to 160–250 mm in diameter.
The content of b-CD immobilised on b-CDP according to
the previous report (33) was 50%.
(2) Krings, U.; Berger, R.G. Appl. Microbiol. Biotechnol. 1998,
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6) Ye, J.D.; Zhou, W.Y. China Patent CN1446789A, 2003.
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Patent CN1749231A, 2006.
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.3 Catalyst characterisation
(
(
8) Cui, J.G.; Wang, C.S.; Liao, X.H. Chem. World. 2002, 6,
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The FTIR spectra of samples were measured by KBr
pellet. All the infrared spectra were recorded on a Bruker
TENSOR 37 FTIR spectrometer with wavenumber
(
2
1
ranging from 400 to 4000 cm
2
and a resolution of
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.
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4.4 Catalyst evaluation
For a typical reaction run, 1 mmol cinnamaldehyde was
dissolved in 25 ml of deionised water at 708C, and 1 g of
b-CDP was added into a 100-ml three-necked flask fitted
with a reflux condenser and magnetic stirrer. The mixture
was heated to 708C in an oil bath with electric heater and
then 4 ml of 7.5% NaClO was slowly dropped in.
The resulting system was stirred with magnetic stirrer at
(
13) Rao, K.R.; Nageswar, Y.V.D.; Kumar, H.M.S. Tetrahedron
Lett. 1991, 32, 6611–6612.
(14) Surendra, K.; Krishnaveni, N.S.; Mahesh, A.; Rao, K.R.
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(
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08C for 2 h. After reaction, the mixture was extracted by
(
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19) Hedges, A.R. Chem. Rev. 1998, 98, 2035–2044.
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ethyl acetate and then centrifuged. The extracted liquid
mixture was analysed by GC-MS with naphthalene as an
internal standard. The reproducibility for the data was
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(
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4
.5 Large-scale experiment
(
(
24) Chung, W.S.; Wang, N.J.; Liu, Y.D.; Leu, Y.J.;
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the following optimum reaction conditions: a mixture of
b-CDP (10 g) and 250 ml deionised water was stirred at
3
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7
08C. Subsequently, cinnamaldehyde (10 mmol) was
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added. After 1 h, 40 ml of 7.5% NaClO was added in
drops to the reaction system and then stirred for 2 h. After
the reaction, the solution was extracted by ethyl acetate,
and benzaldehyde was obtained by distillation.
(
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Acknowledgements
The authors thank the National Natural Science Foundation of
China (Nos 21036009 and 21176268), Guangdong provincial
universities for higher-level talent project and the Fundamental
Research Funds and the Central Universities for providing
financial support to this project.
1
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