Modification of poly(vinyl chloride) with pendant metal complex for catalytic applications

Article abstract of DOI:10.1016/j.crci.2013.03.013

Poly(vinyl chloride) was modified to develop an alternative support for the preparation of polymer-supported catalysts. Commercially available poly(vinyl chloride) was synthetically modified to a polymer containing pendant primary amino groups. The Schiff-base of salicylaldehyde and the amino polymer were prepared and were used as the ligands in the synthesis of a polymer-supported copper complex. The polymer-supported ligand and catalysts were characterized by various physical methods. The polymer with the pendant copper complex was able to catalyze the one-pot three-component Mannich reaction between aldehydes, ketones and anilines under mild and environmentally friendly conditions. The catalyst can be recovered by simple filtration and is reusable.

Full text of DOI:10.1016/j.crci.2013.03.013

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Full paper/Memoire
Modification of poly(vinyl chloride) with pendant metal complex for
catalytic applications
a
Gopalakrishnapanicker Rajesh Krishnan a,b, , Modiyuzhathil K. Sreeraj ,
*
Krishnapillai Sreekumar a
a Department of Applied Chemistry, Cochin University of Science and Technology, Kochi, Kerala, India
b Department of Biomedical Engineering, University at Buffalo, State University of New York, Buffalo, New York, USA
A R T I C L E I N F O
A B S T R A C T
Article history:
Poly(vinyl chloride) was modified to develop an alternative support for the preparation of
polymer-supported catalysts. Commercially available poly(vinyl chloride) was synthe-
tically modified to a polymer containing pendant primary amino groups. The Schiff-base of
salicylaldehyde and the amino polymer were prepared and were used as the ligands in the
synthesis of a polymer-supported copper complex. The polymer-supported ligand and
catalysts were characterized by various physical methods. The polymer with the pendant
copper complex was able to catalyze the one-pot three-component Mannich reaction
between aldehydes, ketones and anilines under mild and environmentally friendly
conditions. The catalyst can be recovered by simple filtration and is reusable.
Received 27 May 2012
Accepted after revision 26 March 2013
Available online xxx
Keywords:
Copper complex
Green chemistry
Mannich reaction
Polymer-supported catalyst
Poly(vinyl chloride)
Schiff base
´
ß 2013 Academie des sciences. Published by Elsevier Masson SAS. All rights reserved.
1. Introduction
of supported species compared with low molecular weight
species, chemical differences, such as prolonged activity or
Catalysis has proved to be very effective in making
processes faster, with a reduced number of synthetic steps,
more selective, and characterized by simpler waste
disposal and improved safety. Apart from increasing
selectivity, the use of catalysts results in easier isolation
and purification of final products. Catalysis is an important
tool in both the development of sustainable process for
chemical transformations and waste minimization during
these transformations [1–3].
Among various types of catalysts, polymer-supported
ones play an important role in synthetic chemistry. They
are associated with a number of advantages over conven-
tional homogenous catalysts. The ease of separation of the
supported species from a reaction mixture by filtration and
washing, the reuse of a catalyst after regeneration, their
adaptability to continuous flow processes and hence, the
use in automated synthesis, the reduced toxicity and odor
altered selectivity of a catalyst in supported form
compared with its soluble analogue are some of them
[4–9]. The polymeric catalysts also represent one of the
most powerful tools for ‘‘green’’ sustainable chemistry, in
the sense that they can be easily recovered and reused
several times [10]. But the disadvantages include high cost
and low loading of commercially available polymer
supports and polymer-supported catalysts. These two
drawbacks prevent their widespread applications in
industrial processes. In this communication, we describe
the development of a high-loading polymer-supported
catalyst derived from one of the cheapest polymers
available, i.e. poly(vinyl chloride) (PVC).
PVC is the most important of the vinyl thermoplastics,
considering the volume of production and field of
applications [11]. PVC is widely used for many purposes,
ranging from building materials to healthcare products
[12,13]. But, the applications of PVC in organic synthesis
and as a support for the catalysts are rarely reported in the
literature, but are gaining interest nowadays [14–19]. In
this article, the preparation of a copper complex using PVC
* Corresponding author.
E-mail address: drgrkrishnan@gmail.com (G.R. Krishnan).
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.2013.03.013
Please cite this article in press as: Krishnan GR, et al. Modification of poly(vinyl chloride) with pendant metal complex
for catalytic applications. C. R. Chimie (2013), http://dx.doi.org/10.1016/j.crci.2013.03.013

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30 oC, 2h
NH2
as a support is reported and this polymer-supported metal
complex was found to be catalytically active in one of the
most important reactions in organic chemistry, i.e. the
*
*
H2N
*
*
n
n
Cl
HN
3
2
1
Mannich reaction. As
a classical reaction in organic
NH2
chemistry, the Mannich reaction found widespread
applications in synthetic and medicinal chemistry [20–
29]. Even though a number of catalysts were reported for
Mannich reactions, only few of them are polymer-
supported. One important example of polymer-supported
catalysts for the Mannich reaction was the polystyrene-
supported BINAP-Pd complex reported by Fujii and
Sodeoka [30]. Another example of polymer-supported
catalysts for Mannich reactions was reported by Lee and
Lee and includes ytterbium triflate supported on a poly(4-
vinylpyridine/styrene) copolymer [31]. They used the
Scheme 1. Synthesis of poly(vinyl chloride) with pendant amino groups.
chemicals and solvents were obtained from commercial
sources and used as received.
2.2. Characterization
FTIR spectra were recorded with a JASCO model 4100
FTIR spectrometer on KBr pellets. 1H NMR spectra were
recorded on a Bruker 300 MHz or 400 MHz instrument
with TMS as the internal standard in CDCl3 (from NMR
Research Centre, IISC, Bangalore). TG–DTA analysis was
done using a PerkinElmer Diamond model TG/DTA system
using platinum as the standard. ICP-AES spectra were
recorded with a Thermo Electron IRIS Intrepid II XSP DUO
model spectrometer. SEM images were recorded on a Jeol
Model JSM-6390LV microscope. The sample was mounted
on a carbon tape and coated with a thin film of gold before
analysis.
catalysts in the synthesis of
a small library of b-
aminoketones from aldehydes, amines and preformed
enols and the yield of the products vary from 84 to 97%.
Other examples of polymer-supported catalysts used for
Mannich reactions include dicyanoketene acetals sup-
ported on an ethyleneglycol dimethacrylate polymer,
polystyrene-supported sulphonic acids, polystyrene-sup-
ported hydroxyprolines and polystyrene-supported scan-
dium triflate [32–35]. But most of these methods included
preformed enols or Schiff-bases as the reactants. Addi-
tionally, the supports used were either commercial
polystyrene or polymers prepared from costly monomers.
The present work attempts to eliminate these challenges
and uses a combination of a reusable catalyst made from a
cheap polymer and ecofriendly solvents for three-compo-
nent Mannich reactions. The catalyst is a PVC-supported
Schiff-base copper complex. The Schiff-base metal com-
plexes are a class of compounds that have been studied
extensively because of their attractive chemical and
physical properties and their wide-ranging applications,
especially in catalysis [36–38].
2.3. Preparation of the polymer with amino groups (3)
PVC (1) (2 g, 31 mmol Cl) was suspended in ethylene
diamine (2) (10.7 mL, 159.8 mmol) taken in a 50-mL
round-bottom flask. The reaction mixture was stirred at
room temperature for 2 h (Scheme 1). The light yellow
colored polymer (3) was collected by filtration and washed
with water (20 mL ꢀ 5 times) and a water–methanol
mixture (2:1 v/v, 20 mL ꢀ 3 times). It was dried under
vacuum at room temperature overnight. Yield = 1.93 g.
FTIR (KBr) nmax cmꢁ1: 3350, 3310 (NH2), 2900 (CH2),
1590 (N–H) and 1465 (CH2).
2. Experimental
2.4. Preparation of the polymer-supported Schiff-base (5)
2.1. Materials
The polymer (3) (2 g, 22 mmol NH2 groups) was
suspended in absolute ethanol (20 mL) taken in a 100-
mL round-bottom flask. Salicylaldehyde (4) (2.6 mL,
24 mmol) was added to it, followed by acetic acid
(0.2 mL). The reaction mixture was refluxed under stirring
for 24 h (Scheme 2). The bright yellow polymer (5) was
collected by filtration and washed with hexane (5 mL ꢀ 5
times), water–methanol (2:1 v/v, 20 mL ꢀ 3 times) and
Benzaldehyde, salicylaldehyde and cyclohexanone
were purchased from S. D. Fine Chemicals (India) and
were purified according to the standard procedures. 3-
Nitro benzaldehyde and 4-nitro aniline were purchased
from Lancaster Synthesis (UK) and were used as received.
PVC (high molecular weight, K value 69–71) was pur-
chased from Fluka and used as received. All the other
*
*
n
NH HN
CHO
*
EtOH, reflux, 24 h
OH
*
n
N
N
HN
3
NH2
4
OH
HO
5
Scheme 2. General method for the synthesis of the polymer-supported Schiff-base.
Please cite this article in press as: Krishnan GR, et al. Modification of poly(vinyl chloride) with pendant metal complex
for catalytic applications. C. R. Chimie (2013), http://dx.doi.org/10.1016/j.crci.2013.03.013

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3
*
*
n
*
*
n
NH HN
Cu
NH HN
CH3OH, 3 h
Cu(CH3COO)2
reflux
N
O
N
O
N
N
OH
HO
5
6
Scheme 3. General method for the synthesis of the polymer-supported copper complex.
water (20 mL ꢀ 5 times). It was dried under vacuum at
room temperature overnight. Yield = 1.90 g.
FTIR (KBr) nmax cmꢁ1: 3600 (O–H), 3064 (aromatic),
2900 (CH2), 1680 (C5N) and 1463 (CH2); 1H NMR
and washed with ethanol. The filtrate and washings were
combined. The solvent was removed under vacuum and
the pure product was isolated by column chromatography
on silica gel using the hexane–ethyl acetate mixture (20:1
(300 MHz, CDCl3):
d
1.27–1.76 (CH2, polymer chain),
v/v) as the eluent. The b-amino ketones (10) were
2.02 (NH, br), 2.56–2.86 (CH, polymer), 3.00 (CH2, CH2–
NH–), 3.59 (CH2, CH2–N5CH), 5.5 (OH), 6.73–7.42 (aro-
matic), 8.0 (CH5N),
previously reported compounds and were characterized
by FTIR and 1H NMR spectroscopy. The characterization
data of some of the representative compounds are given
below. Characterization data of other compounds are given
as supplementary material.
2.5. Preparation of the copper (II) complex of the polymer-
supported Schiff-base (6)
2.7. 2-[10-(N-phenylamino)-10-
The polymer-supported Schiff-base (5) (2 g, 10 mmol),
Cu(CH3COO)2 (0.90 g, 5 mmol) and 20 mL of methanol
were added into a 50-mL round-bottom flask. The reaction
mixture was refluxed for 12 h (Scheme 3). The yellowish
polymer with a blue tinge (6) was collected by filtration,
washed with water (20 mL ꢀ 5 times), a water–methanol
mixture (2:1 v/v, 20 mL ꢀ 3 times) and dried under
vacuum at room temperature overnight. Yield = 1.75 g.
(phenyl)]methylcyclohexanone (Table 3, Entry 1)
FTIR (KBr) nmax cmꢁ1: 3328, 3021, 2932, 2858, 1702,
1590, 1520, 1495, 1300; 1H NMR (400 MHz, CDCl3):
d 1.73–
1.81 (m, 2H), 1.91–1.98 (m, 4H), 2.36–2.38 (m, 1H), 2.45–
2.49 (m, 1H), 2.73–2.77 (m, 1H), 4.63 (d, J = 6.81 Hz, 1H),
4.74 (s, 1H), 6.52 (d, J = 7.73 Hz, 2H), 6.63 (t, J = 7.26 Hz, 1H),
7.06 (t, J = 7.37 Hz, 2H), 7.24 (t, J = 6.30 Hz, 1H), 7.33 (t,
J = 6.76 Hz, 2H), 7.40 (d, J = 7.09 Hz, 2H).
FTIR (KBr)
(C5N), 1462 (CH2) and 635 (Cu-N); 1H NMR (300 MHz,
CDCl3): 1.27–1.76 (CH2, polymer chain), 2.02 (NH, br),
n
max cmꢁ1: 3064 (aromatic), 2900 (CH2), 1642
d
2.8. 2-[10-(N-phenylamino)-10-(4-
2.56–2.86 (CH, polymer), 3.00 (CH2, CH2–NH–), 3.59 (CH2,
CH2–N5CH), 6.73–7.42 (aromatic), 8.0 (CH5N).
ICP-AES analysis of the complex showed that the
loading of the metal ion was 4.26 mmol/g of the polymer.
nitrophenyl)]methylcyclohexanone (Table 3, Entry 4)
FTIR (KBr)
n
max cmꢁ1: 3386, 3021, 1673, 1527, 1348; 1H
1.58–1.66 (m, 2H), 1.75–1.79 (m,
NMR (400 MHz, CDCl3):
d
1H), 1.95–2.08 (m, 3H), 2.34–2.42 (m, 2H), 2.86–2.89 (m,
1H), 4.59 (s, br, 1H), 4.84 (d, J = 5.2 Hz, 1H), 6.52–6.54 (d,
J = 8.0 Hz, 2H), 6.66–6.70 (m, 1H), 7.08–7.12 (t, J = 8.0 Hz,
2H), 7.45–7.49 (t, J = 8.0 Hz, 1H), 7.77–7.80(m, 1H), 8.07–
8.09 (d, J = 8.0 Hz, 1H), 8.24–8.26 (d, J = 7.6 Hz, 1H).
2.6. General procedure for three-component Mannich
reaction
A
50-mL round-bottom flask was charged with
aldehyde (7) (5 mmol), aniline (8) (5.1 mmol), ketone (9)
(5 mmol) and ethanol (5 mL). To it, the polymer-supported
catalyst (6) (58.67 mg, 5 mol% of Cu) was added. The
reaction mixture was stirred at room temperature (Scheme
4). The progress of the reaction was monitored by thin
layer chromatography on a silica gel plate using a hexane–
ethyl acetate mixture (25:1 v/v) as the mobile phase. After
the completion of the reaction, the catalyst was filtered
2.9. General procedure for recycling the catalyst
The catalyst (6) used for first cycle of reaction was
washed carefully with ethanol (5 mL ꢀ 5 times) and water
(5 mL ꢀ 5 times) and was dried under vacuum at room
temperature for 24 h. It was reused for the successive
reaction cycles.
3. Results and discussion
R2
O
NH2
NH
O
3.1. Synthesis of the polymer with pendant metal complex
Polymer (6)
R1
R1 CHO
7
EtOH, 6-10 h
The polyethylene chain having a pendant Schiff-base
metal complex was prepared using a three-step synthetic
method, which was reported by us previously [14]. A more
detailed characterization of the catalyst is included in the
following section.
R2
55-86%
8
9
10
Scheme 4. Three-component Mannich reaction catalyzed by the
polymer-supported copper complex.
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In the first step, commercially available PVC (1) was
converted into a polymer carrying pendant primary amino
groups (3) using a standard procedure. The reaction is
shown in Scheme 1. For this, PVC was treated with an
excess amount of ethylene diamine (2) at room tempera-
ture. An excess amount of ethylene diamine could prevent
cross-linking between different polymer chains as well as
the formation of cyclic derivatives by the condensation of
the two primary amino groups of single ethylene diamine
molecule with neighboring chlorine atoms. After this
reaction, the color of the polymer was changed from white
to light yellow. The FTIR spectrum of the aminated polymer
(3) showed the appearance of peaks at 3350, 3310 and
Comparison of the FTIR spectra of the polymers (5) and
(6) revealed that the peaks corresponding to the hydroxyl
group of salicylaldehyde disappeared in the spectrum of
(6). Additionally, the peak due to C5N stretching under-
went a blue shift of 52 cm–1 and occupies a new position at
1642 cmꢁ1 in the case of (6). The appearance of a new band
at 635 cmꢁ1 due to the Cu–N bond also confirmed the
formation of the Cu complex [38]. 1H NMR analysis of the
polymer (6) (Fig. 1B) showed that the peak corresponding
to the phenol group of salicylaldehyde disappeared while
the other peaks remained unaltered compared to the
spectrum of the polymer (5). The electronic spectra of the
complex showed two bands at 422 and 543 nm, which
were assigned to the charge-transfer transitions and d–d
transitions, respectively. The thermogravimetric analysis
showed that the polymer (6) underwent decomposition in
the 160–175 8C temperature range, while PVC remained
thermally stable up to a temperature of 200 8C. The
thermal stability of (6) around 100 8C clearly indicates that
there is no water molecules associated with the copper
complex. From the thermal analysis data, it was observed
that after the formation of the metal-containing pendant
group, the thermal stability of the polymer decreased,
which might be due to the thermal decomposition of the
pendant group. From these analytical data, the structure of
the copper complex attached to the polymer backbone is
assumed to be a square planar one, as shown in Scheme 3.
A SEM image of the polymer (6) is shown on Fig. 2. It clearly
indicates a highly coiled structure of the polymer with high
surface area. The solubility profile of the polymer (6)
showed that it is insoluble in solvents, like water, ethanol
and methanol, while it is soluble in chloroform.
1590 cmꢁ1
, which were assigned to be due to the
stretching and bending vibrations of the primary amino
groups, respectively. CHN analysis and estimation of the
primary amino groups by acid–base titration showed that
the polymer contained 5 mmol of NH2 groups per gram of
resin.
The aminated polymer (3), on reaction with salicylal-
dehyde (4) in the presence of catalytic amounts of acetic
acid in ethanol under refluxing conditions, gave the Schiff-
base of salicylaldehyde attached to the polyethylene
backbone (5). The reaction is shown in Scheme 2. The
color of the polymer turned from light yellow to dark
yellow in the course of the formation of the Schiff-base.
FTIR spectra of (5) showed that the peaks corresponding to
the primary amino groups in the starting polymer had
disappeared and that a new peak appeared at 1680 cmꢁ1
due to C5N stretching vibrations. 1H NMR spectra of (5)
clearly showed peaks in the aromatic region and a broad
peak at 5.2 ppm due to the –OH group of the salicylalde-
hyde moiety (Fig. 1). Elemental analysis also supported the
fact that all of the primary amino groups were converted
into the Schiff-base.
3.2. One-pot three-component Mannich reaction catalyzed
by the polymer-attached Cu complex
Reacting the polymer (5) with Cu(CH3COO)2 in metha-
nol under reflux gave the polymer carrying the pendant
Schiff-base–Cu(II) complex (6). The reaction is shown in
Scheme 3.
The polymer-attached copper complex (6) was used as
a heterogeneous catalyst in the one-pot three-component
Mannich reaction between aldehyde (7), amines (8) and
Fig. 1. NMR spectra of the polymer-supported Schiff-base before (A) and after (B) formation of the complex.
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5
Table 3
Three-component Mannich reactions catalyzed by the polymer-sup-
ported copper complex.
Entry R1
R2
Ketone
Time (h) %Yielda,b
1
2
3
4
5
6
7
8
9
10
C6H5
H
H
H
H
Cyclohexanone 10
Cyclohexanone 10
Cyclohexanone 10
75
85
81
77
86
76
72
55
82
78
4-OCH3C6H4
4-ClC6H4
3-NO2C6H4
Cyclohexanone
8
6
4-OCH3C6H4 4-OCH3 Cyclohexanone
4-OHC6H4
C6H5
4-Cl
4-OCH3 Cyclohexanone 10
4-NO2 Cyclohexanone 10
Cyclohexanone 10
C6H5
C6H5CHCH2 4-OCH3 Cyclohexanone
C4H3S Cyclohexanone
6
8
H
a
Reaction conditions: 5 mmol of aldehyde, 5 mmol of cyclohexanone,
5.2 mmol of aniline, 5 mL of ethanol, catalyst (58.67 mg, 5 mol% of Cu).
b
Isolated yield of the product.
Fig. 2. SEM image of the polymer-supported catalyst.
by simple filtration. In other organic solvents, like 1,4-
dioxane and THF, the catalyst showed poor performance.
The reaction gave quantitative yield when water was used
as the solvent. But the catalytic activity of the present
polymer-supported complex is lower in water compared to
other polymer-supported catalysts reported in the litera-
ture [32,33].
ketones (9) to obtain b-amino ketones (10). The Mannich
reaction between benzaldehyde, aniline and cyclohexa-
none was carried out as a model reaction in ethanol. Since
the catalyst is insoluble in ethanol, carrying out the
reaction in ethanol helps to exploit the advantages of
heterogeneous catalysis. Initially, the model reaction was
carried out in the presence of various amounts of the
catalyst. The results are summarized in Table 1. It can be
seen that only 5 mol% of the catalyst is required to get good
yield in a short period of time.
The results of an investigation on the role of solvent in
catalysis are summarized in Table 2 and showed that the
reaction proceeded quantitatively in solvents, like ethanol,
methanol, and chloroform. Since the catalyst is more
soluble in CHCl3, it is expected that homogeneous catalysis
is more pronounced here. Under such situation, it became
difficult to separate the catalyst from the reaction mixture
In order to prove the efficiency of the catalyst, a family
of aldehydes and anilines were used as substrates along
with cyclohexanone to synthesize a number of
b-amino
carbonyl compounds (Scheme 4). The results are summar-
ized in Table 3. The reaction proceeded smoothly within 6
to 10 h to give the products in good yield in the case of all
the substrates studied. Aromatic aldehydes, carrying
electron-withdrawing groups on the benzene ring, gave
good yields. On the other hand, anilines, carrying electron-
donating groups on the benzene ring, gave better results,
while those carrying electron-withdrawing groups, like
NO2 gave comparatively poor yield. Heterocyclic aldehyde,
like thiophene aldehyde also gave good yields. All the
products were isolated by column chromatography and
characterized using FTIR and 1H NMR spectroscopies.
Catalyst recycling was investigated with the model
reaction under optimized reaction conditions. After the
completion of each reaction cycle, the catalyst was filtered
and washed extensively with ethanol and water and dried
under vacuum at room temperature. This catalyst was used
in the next cycle. It was found that the catalyst remained
active up to four reaction cycles without considerable loss
of activity. There is a small loss of catalytic activity during
the fifth cycle (Table 4).
Table 1
Effect of catalyst loading on the Mannich reaction.
Entry
Amount of catalyst (mol% of Cu)
Time (h)
%Yielda,b
1
2
3
4
5
1
2
3
4
5
24
24
12
12
10
50
62
65
70
75
a
Reaction conditions: 5 mmol of benzaldehyde, 5 mmol of cyclohex-
anone, 5.2 mmol of aniline, 5 mL of ethanol.
b
Isolated yield of the product.
Table 4
Table 2
Effect of recycling on catalysis.
Effect of the solvent on catalysis.
Entry
No. of recycles
Time (h)
%Yielda,b
Entry
Solvents
%Yielda,b
1
2
3
4
5
1
2
3
4
5
10
10
12
12
12
75
75
74
72
68
1
2
3
4
5
Ethanol
Methanol
Water
75
73
70
70
67
CHCl3
CHCl2
a
Reaction conditions: 5 mmol of benzaldehyde, 5 mmol of cyclohex-
a
Reaction conditions: 5 mmol of benzaldehyde, 5 mmol of cyclohex-
anone, 5.2 mmol of aniline, 5 mL of solvent, catalyst, 10 h.
anone, 5.2 mmol of aniline, 5 mL of ethanol, catalyst (58.67 mg, 5 mol% of
Cu).
b
b
Isolated yield of the product.
Isolated yield of the product.
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for catalytic applications. C. R. Chimie (2013), http://dx.doi.org/10.1016/j.crci.2013.03.013

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4. Conclusion
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In conclusion, the copper complex of PVC-supported
salicylaldehyde Schiff’s base was prepared and character-
ized. This polymer-supported complex was found to be an
efficient heterogeneous catalyst in the three-component
Mannich reaction between aldehyde, anilines and ketones.
Various factors influencing the catalytic activity of the
polymer were studied and optimized. A small library of b-
keto amines were prepared to prove the generality of the
catalysis. The catalyst was found to be reusable.
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Appendix A. Supplementary data
Supplementary data associated with this article can be
found, in the online version, at http://dx.doi.org/10.1016/
j.crci.2013.03.013.
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Please cite this article in press as: Krishnan GR, et al. Modification of poly(vinyl chloride) with pendant metal complex
for catalytic applications. C. R. Chimie (2013), http://dx.doi.org/10.1016/j.crci.2013.03.013