Poly(4-vinylpyridine-co-ethylvinylbenzene) as heterogeneous reusable catalyst for the synthesis of benzoyl fumarate

Article abstract of DOI:10.1007/s00706-015-1531-7

Poly(4-vinylpyridine-co-ethylvinylbenzene) 25 % cross-linked (with divinylbenzene) has been found to be an effective heterogeneous catalyst for the synthesis of benzoyl fumarate from aldehyde and dimethyl acetylenedicarboxylate. Various aromatic aldehydes undergo this reaction with good yield in presence of 15 wt% of the catalyst. The catalyst was recovered and reused six times without appreciable alteration in activity.

Full text of DOI:10.1007/s00706-015-1531-7

Monatsh Chem
DOI 10.1007/s00706-015-1531-7
ORIGINAL PAPER
Poly(4-vinylpyridine-co-ethylvinylbenzene) as heterogeneous
reusable catalyst for the synthesis of benzoyl fumarate
Bishwapran Kashyap1 Prodeep Phukan1
•
Received: 14 April 2015 / Accepted: 6 July 2015
Ó Springer-Verlag Wien 2015
Abstract Poly(4-vinylpyridine-co-ethylvinylbenzene) 25 %
cross-linked (with divinylbenzene) has been found to be an
effective heterogeneous catalyst for the synthesis of benzoyl
fumarate from aldehyde and dimethyl acetylenedicarboxy-
late. Various aromatic aldehydes undergo this reaction with
good yield in presence of 15 wt% of the catalyst. The cat-
alyst was recovered and reused six times without
appreciable alteration in activity.
many synthetically important reactions such as Diels–
Alder reaction [1–8]. While studying the photo-oxida-
tion of furans, Scarpati and co-workers have observed
the formation of benzoyl fumarates [9, 10]. In the year
2003, a direct protocol for the synthesis of benzoyl
fumarates was developed independently by Shi and Nair
[11, 12]. Their approach involves the reaction between
aldehyde and dimethyl acetylenedicarboxylate (DMAD)
in presence of Lewis base such as pyridine and DMAP
as catalyst. Recently, Bayat et al. observed the forma-
tion of similar structural features as byproduct during
the synthesis of c-butyrolactone [13]. There are also few
reports in the literature for the synthesis of benzoyl
fumarates [5, 14]. However, all these methods are based
on the application of homogeneous catalysts which have
the obvious problem of reusability. Application of reu-
sable catalyst is important from the industrial as well as
green chemistry point of view. We have recently
reported a homogeneous reusable catalyst for the syn-
thesis of benzoyl fumarates [15]. Subsequently, we
made an improvement of the method by developing a
nicotinic acid-based heterogeneous catalyst [16].
Although we are successful in synthesizing new reusable
catalysts, these catalysts have to be made via multistep
procedure. So, we looked for alternative commercially
available catalyst to make the method more viable.
Since DMAP has been proven to be the best catalyst for
this particular reaction, we intended to examine the
possibility of using poly(4-vinylpyridine-co-ethylvinyl-
benzene) 25 % cross-linked with divinylbenzene as the
first case due to its commercial availability. In this
paper, we describe the use of poly(4-vinylpyridine-co-
ethylvinylbenzene) (PVPEVB) as reusable heterogeneous
catalyst for the synthesis of benzoyl fumarate from
aldehyde (Scheme 1).
Graphical abstract
Keywords Benzoyl fumarate Á
Poly(4-vinylpyridine-co-ethylvinylbenzene) Á
Heterogeneous catalyst Á DMAD Á Aldehyde
Introduction
Benzoyl fumarates and their corresponding acids are
known to be the vital precursors in the synthesis of
many important agrochemicals, drugs as well as in
Electronic supplementary material The online version of this
article (doi:10.1007/s00706-015-1531-7) contains supplementary
material, which is available to authorized users.
& Prodeep Phukan
pphukan@yahoo.com
1
Department of Chemistry, Gauhati University, Guwahati,
Assam 781014, India
123

B. Kashyap, P. Phukan
Scheme 1
temperature for an appropriate time. After the completion
of the reaction (as indicated by TLC analysis), the catalyst
was separated by filtration and washed with a small amount
of DCM. The reaction mixture was concentrated and the
crude material was purified by column chromatography
using a mixture of petroleum ether and ethyl acetate as
eluent to get the pure product. Initial reaction in the
absence of the catalyst fails to give the desired product
even after 24 h of reaction (Table 1, entry 1). However,
5 wt% of catalyst and DME as solvent gives 70 % of
benzoyl fumarate as product with 10 h of reaction time
(Table 1, entry 2). It was observed that the reaction in other
solvents such as acetonitrile and THF produced lower yield
with longer reaction hours (Table 1, entries 3, 4). Only
trace amount of the product formation was observed when
DCM was used as solvent (Table 1, entry 5). The reaction
was further investigated by increasing the catalyst amount.
The reaction in presence of 15 wt% of PVPEVB produced
80 % of corresponding fumarate after 8 h of reaction
(Table 1, entry 7). Further increase in catalyst loading did
not improve the reaction (Table 1, entries 8, 9). Finally,
Results and discussion
The catalyst, PVPEVB (Fig. 1) is commercially avail-
able. Initially, the reaction between 4-nitrobenzaldehyde
and DMAD was taken as a model reaction to find out the
optimum condition for the reaction. In a typical reaction,
5 wt% (based on the aldehyde amount) of the catalyst was
added to a mixture of 4-nitrobenzaldehyde (1 mmol) and
DMAD (1 mmol) in 5 cm3 DME at 0 °C under nitrogen
atmosphere and the reaction was continued at room
Fig. 1 Structure of poly(4-vinylpyridine-co-ethylvinylbenzene),
25 % cross-linked with divinylbenzene (as per Sigma-Aldrich cata-
logue description)
Table 1 Reaction of p-nitrobenzaldehyde with DMAD catalyzed by PVPEVB under different conditions
Entry
PVPEVB/wt%
Solvent
Time/h
Yield/%a
1
2
3
4
5
6
7
8
9
0
5
DME
DME
THF
24
10
14
24
24
8
0
70
50
37
Trace
74
80
80
81
5
5
CH3CN
DCM
DME
DME
DME
DME
5
10
15
20
25
8
8
8
Reaction conditions: 4-nitrobenzaldehyde (1 mmol), DMAD (1 mmol), 5 cm3 solvent, 0 °C to rt
a
Isolated yield
123

Poly(4-vinylpyridine-co-ethylvinylbenzene) as heterogeneous reusable catalyst for the…
Table 2 Synthesis of benzoyl fumarates using PVPEVB catalyst
Entry
Ar
Yield/%a
1
2
C6H5 (1a)
4-BrC6H4 (1b)
4-ClC6H4 (1c)
4-FC6H4 (1d)
60
79
74
70
80
68
53
61
68
70
3
4
5
4-NO2C6H4 (1e)
4-MeOC6H4 (1f)
4-MeC6H4 (1g)
6
7
8
C10H7 (1h)
9
3-BrC6H4 (1i)
3-ClC6H4 (1j)
10
Reaction conditions: aldehyde (1 mmol), DMAD (1 mmol), PVPEVB (15 wt%), 5 cm3 DME, 0 °C to rt, 8 h
a
Isolated yield
Table 3 Reusability of the catalyst
15 wt% of catalyst (based on the aldehyde amount),
1 mmol of aldehyde, 1 mmol of DMAD in DME and 8 h
of reaction time was found to be the optimum condition for
the reaction. After optimization the protocol has been
extended to a variety of aldehydes and the results are
presented in Table 2.
Entry
Catalyst reused
Catalyst recovered/%a
Yield/%b
1
2
3
4
5
6
1st
98
97
95
92
91
89
80
79
79
78
77
76
2nd
3rd
4th
5th
6th
The efficiency of this method is evident from the high
yield of benzoyl fumarates formed from various substituted
benzaldehydes. It was observed that the presence of elec-
tron withdrawing group enhances the yield of the reaction
(Table 2, entries 2–6). On the other hand, electron donating
group results in the lower product yield (Table 2, entry 7).
It was further observed that para-substituted aldehyde
shows better results compared to the corresponding meta-
substituted aldehyde (Table 2, entries 3, 4, 8, 9). This
reaction was found to be less effective for aliphatic
aldehyde.
Reaction conditions: 4-nitrobenzaldehyde (1 mmol), DMAD
(1 mmol), 5 cm3 DME, 0 °C to rt, 8 h
a
With respect to first use
b
Isolated yield
decrease in the catalyst recovery. After the sixth run, the
yield was found to be 76 with 89 % of catalyst recovery
(Table 3, entry 6).
Reusability of the catalyst was tested with 4-nitrobenz-
aldehyde. After the completion of the reaction, the solvent
was removed and 5 cm3 DCM was added to the crude
reaction mixture. The reaction mixture was passed
through a filter paper to remove the insoluble polymeric
catalyst. The residue in the filter paper was washed with
DCM, dried under vacuum, and kept in a desiccator for
24 h before reuse. Initially, after the first use, the recovery
percentage of the catalyst was found to be 98 % in
comparison to the first use of the catalyst. The recovered
catalyst was reused. We have reused the catalyst six times
without appreciable loss in activity. The slight decrease in
yield in the subsequent step can be attributed to the small
The mechanism of this reaction has already been pro-
posed by Shi et al. [11]. In this case, the pyridine moiety
attached to the polymer takes part in the mechanism.
Thus, the pyridine subunit of the polymeric catalyst pro-
duces a zwitterionic intermediate by interacting with
DMAD, which subsequently reacts with aldehyde fol-
lowed by intermolecular proton transfer. Expulsion of the
catalyst at the final stage results in the formation of the
product.
In conclusion, we have developed an efficient heteroge-
neous and reusable catalytic protocol for the synthesis of
benzoyl fumarate from aldehyde and DMAD in presence of
123

B. Kashyap, P. Phukan
a catalytic amount of poly(4-vinylpyridine-co-ethylvinyl-
benzene). Use of a commercially available catalyst makes
this methodology convenient for direct applications. The
method is suitable for various aromatic aldehydes to obtain
the product in high yield. Moreover, the catalyst can be
reused six times without appreciable loss in activity.
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The catalyst poly(4-vinylpyridine-co-ethylvinylbenzene)
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Typical experimental procedure for polymer
catalyzed synthesis of benzoyl fumarate
A solution of 0.142 g DMAD (1 mmol) and 0.045 g
4-nitrobenzaldehyde (1 mmol) in 5 cm3 anhydrous DME
was cooled to 0 °C under nitrogen atmosphere. PVPEVB
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Acknowledgments Financial Support from University Grants
Commission, India (Grant No. 41-206/2012/SR), India, is gratefully
acknowledged. BK thanks CSIR for the senior research fellowship.
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123