Polystyrene supported palladium nanoparticles catalyzed cinnamic acid synthesis using maleic anhydride as a substitute for acrylic acid

Article abstract of DOI:10.1039/c7cy01126a

Maleic anhydride was explored as a substitute for acrylic acid to synthesize cinnamic acids from aryl halides under heterogeneous palladium catalyzed conditions. The combined role of surface and impregnated catalyst together performed an upright engineering to hold in situ generated molecules on the surface and subsequently facilitate their interaction for the desired product synthesis. Overall, a surface mediated approach for cinnamic acid synthesis from maleic anhydride following a major unexplored pathway through catalyst promoted decarboxylation was critically investigated.

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Polystyrene Supported Palladium Nanoparticles Catalyzed
Cinnamic Acid Synthesis using Maleic Anhydride as Substitute of
Acrylic Acid
Received 00th January 20xx,
Accepted 00th January 20xx
Vandna Thakur,a,b,† Sandeep Kumara,b,† and Pralay Das*a,b
DOI: 10.1039/x0xx00000x
www.rsc.org/
Maleic anhydride was explored as a substitute of acrylic acid to Diels-Alder reaction to generate different molecules9
synthesize cinnamic acids from aryl halides under heterogeneous polymerized products,10 and ligand for synthesis of
palladium catalyzed conditions. The combined role of surface and organometallics.11 The synthesis of phenylmaleic anhydride
impregnated catalyst together performed upright engineering to and its derivatives by oxidative Heck reaction using maleic
hold in situ generated substrates on the surface and simultaneous anhydride has also been achieved.12 The synthesis of cinnamic
catalytic interaction for desired product formation. Overall, a acid having broad spectrum of biological activities13 can be
surface mediated approach for cinnamic acid synthesis from carried out by condensation14 and Heck cross coupling
maleic anhydride following a major unexplored pathway through approaches. Numerous protocols have been reported using
catalyst promoted decarboxylation was critically investigated.
acrylic acid as coupling partner with aryl halides and
pseudohalides using homogeneous as well as heterogeneous
palladium catalyst.15,16
In recent research, collective role of surface and impregnated
transition metal nanoparticles has been investigated
assertively in the development of sustainable synthetic
methods for various organic transformations.1 A number of
factors including the size and morphology of metal
nanoparticles (NPs),2 the nature of stabilizing agent and its
interaction with substrates/metal play crucial rule in
influencing the reaction.3 The extensively used catalyst
supports like carbon materials (carbon, graphene and carbon
nanotubes), polymers and metal oxides (silica, alumina and
titania) are well known for facilitating the plethora of
reactions.4
To the best of our knowledge, all the methods involve the use
of acrylic acid as reagent that is liquid, difficult to handle and
usually supplied with free radical inhibitor to stop the
polymerization. From the studies so far, it is clear that no
stable and easy to handle substitute for acrylic acid is available
as
a coupling partner for the cinnamic acid synthesis.
Numerous efforts have been made by our group to use the
polymer surface having both anchoring ability of ionic
compounds in outer sphere and holding ability of discharged
molecules in inner core which helps catalyst to perform
extraordinarily for carboxylation, esterification and
cycloaddition reactions.17
The tandem reactions of easily available, less volatile, stable
reagents is a strong alternative for the synthesis of valuable
products5 and number of methods have been reported such
as phenylpropiolic acid for phenyl acetylene, acetylide lithium,
calcium carbide for acetylene and carbonylating precursors for
CO gas.6-8 We envisaged that commercially available maleic
anhydride having high melting and boiling point can be a
substitute for acrylic acid to synthesize cinnamic acids
following coupling approaches.
In context of our investigations for exploration of small
molecules as substrate in organic synthesis, herein we report a
bench stable, low cost and easy to handle maleic anhydride as
substitute for acrylic acid to synthesize cinnamic acids from
aryl halides following consecutive approach over polystyrene
supported palladium (Pd@PS) surface.
We have developed Pd@PS catalyst following reduction
deposition approach of Amberlite IRA 900 Cl- form resin
+
(polystyrene-NR3 Cl-) as PS and Pd(OAc)2 as metal precursor.
Till date, maleic anhydride has been used as substrate for
-
The PS was partially exchanged with borohydride (BH4 ) ions
and used for in situ reduction of Pd(II) into Pd(0) and
simultaneously impregnation on the polystyrene support to
produce Pd@PS catalyst (supplementary information, ESI). The
Pd@PS was well characterized by scanning electron
microscopy (SEM), transmission electron microscopy (TEM)
studies, powder X-ray diffraction (pXRD), (Figure 1).17c,18 The
a.Address here. Natural Product Chemistry & Process Development Division, CSIR-
Institute of Himalayan Bioresource Technology, Palampur-176061, (H. P.), India.
E-mail: pdas_nbu@yahoo.com, pdas@ihbt.res.in.
b.Academy of Scientific & Innovative Research, New Delhi, India
† These authors contributed equally
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
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Previous work: Heck cross-coupling approach:
Table 1. Optimization of Reaction Conditions for the Synthesis of Cinnamic Acids
R
R
R
O
N2BF4
or
Pd(OAc)2/Pd(dba)3
(a)
O
+
NaOAc/Li2CO3
R
O
O
O
O
O
O
O
O
Ref:[13b]
X
CO2H
1) PdCl2, Ph3P
+
O
(b)
R
2) Ac2O, 100 oC or
200-300 oC, 0.5-2 Torr
HO2C
R
O
Ref:[13c]
Our work: Synthesis of cinnamic acid derivatives:
O
X
CO2H
Pd@PS, K2CO3
(c)
+
R
R
O
PEG-400:1,4-dioxane (1:1)
125 oC, 12 h
O
Scheme 1. Comparative Study of Pd-Catalyzed Heck Reaction
SEM and SEM-EDS studies were conducted to reveal the
dispersion of Pd NPs in the matrix. TEM analysis of Pd@PS was
performed for particle size distribution and crystal structure
determination (Figure 1). Also, the HRTEM analysis for crystal
structure determination showed the interplaner distance of
0.22 nm corresponding to (111) plane of face centered cubic
Pd (Figure 1d). The largest average number of NPs has the
particle size in range of 1-4 nm as calculated from TEM image.
(Figure 1f). The powder XRD study revealed the presence of
(111) and (200) planes in the Pd@PS catalyst. The developed
Pd@PS catalyst was applied in the reaction of aryl halides and
maleic anhydride for the synthesis of cinnamic acids.
aReaction conditions: 1a (0.46 mmol), 2 (1.37 mmol), Pd@PS (as stated), solvent
(2 mL), PEG-400:1,4-dioxane (1:1); isolated yields; bmaleic anhydride (0.55 mmol
); cmaleic anhydride (0.92 mmol); dmaleic anhydride (2.3 mmol); n.r. = no reaction
The screening studies were initiated using 4-iodotoluene 1a as
model substrate, maleic anhydride
2 and different reagent
conditions. The screening of the solvents showed that DMF
(Table 1, entry 3) and the mixture of PEG-400 and 1,4-
dioxane(1:1) (Table 1, entry 4) afforded the desired product in
approximately equal yield. But the mixture of PEG-400 and 1,4-
dioxane (1:1) was preferred considering environmental
benignity. The different conditions such as catalyst loading
(Table 1, entries 4-6), time of the reaction (Table 1, entries 7-
8), temperature (Table 1 entries 9-10) and organic/inorganic
bases were also screened (Table 1, entry 11-12). The quantity
of maleic anhydride also affected the reaction yield (Table 1,
entries 13-15). The change in quantity of base did not
improved the product yield (Table 1, entry 16-17). The
commercially available Pd/C and Pd(OAc)2 afforded the desired
product in 12 and 16% yields respectively (Table 1, entries 18-
19). No product formation was observed in the absence of
base and in the presence of acetic acid (Table 1, entries 20-21).
Moreover, the reaction did not occur in the absence of Pd@PS
catalyst (Table 1, entry 22). Finally, the conditions:
1 (1 equiv.),
Figure 1. (a) SEM (b) SEM-EDS (c) TEM at 20 nm (d) HRTEM at 1 nm showing lattice
fringe spacing (e) FFT of selected region from (d), (f) Particle size distribution histogram
as calculated from (c), (g) XRD pattern of Pd@PS catalyst.
2
(3 equiv.), Pd@PS (3 mol %) and K2CO3 (1 equiv.) in (1:1)
o
mixture of PEG-400 and 1,4-dioxane (2 mL) at 125 C for 12 h
gave the best results and were chosen as optimized reaction
conditions 3a (Table 1, entry 4).
2 | J. Name., 2012, 00, 1-3
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However, the optimization studies revealed that said reaction out in the presence of Pd@PS, K2CO3 and PS (Scheme 2, ‘c’,
was feasible only in the presence of Pd@PS while Pd/C and Path-I, II and III). To our delight, the decarboxylation reaction is
Pd(OAc)2 did not promote the reaction well (Table 1). These possible only in the presence of Pd@PS catalyst (Scheme 2, ‘c’,
findings provided the thrust to investigate the role of Pd metal Path-I) while the reaction with K2CO3 and PS was unsuccessful
and the support (PS) in the reaction. We envisaged that the PS (Scheme 2, ‘c’, Path-II and III) emphasizing the fact that Pd is
containing quaternary amine (-R3N+Cl־) units might play a playing crucial role in the decarboxylation reaction. But the
crucial anchoring role through partial exchange with the reaction of intermediate
5 with Pd@PS afforded the product
maleic acid, the hydrolyzed product of maleic anhydride. This 3g in poor yield (56%) (Scheme 2) which indicated the
helps to bring maleic acid in close proximity of Pd metal coexistence of other reaction pathway. As per the literature
catalyst bound over the same hydrophobic surface which reports, maleic acid is prone to decarboxylation at
o
facilitate the reaction. The FT-IR studies were conducted to temperature higher than 130 C into acrylic acid (Scheme 3).19
further support our assumption. The FT-IR analysis of maleic Also, the interaction of support (PS) with maleic acid may
acid, Polymer Support (PS) (Figure S1, ‘a’ and ‘b’ respectively, assist the decarboxylation process to give in situ acrylic acid.
ESI), PS after treating with maleic anhydride for 1 h (Figure S1, However, we were unable to detect the formation of acrylic
‘c’, ESI), Pd@PS (Figure S1, ‘d’, ESI) and Pd@PS after treating acid with GC, HPLC and NMR techniques, while the reaction of
with maleic anhydride for 1h (Figure S1, ‘e’, ESI), was 1g with acrylic acid (3 equiv.) under standard reaction
performed (Figure S1, ESI). New intense peaks in the 1600- conditions gave the desired product 3g in higher yield (86%) in
1200 cm-1 region were observed in IR spectra ‘c’ and ‘e’ which 6 h (Scheme 2, ‘d’).
could be attributed to the interaction of maleic acid with the
> 130 o
[Ref. 16]
C
‘PS’ (Figure S1, ESI). To further establish the claim, the
exchanged Pd@PS (after washing) was successfully used in the
reaction with 1a to afford the desired product 3a and IR study
of Pd@PS after reaction also showed disappearance of IR
peaks in 1600-1200 cm-1 region, clearly indicating that the
reaction occurs over the surface (Figure S2, ESI).
COOH
Decomposition in solution
O
O
O
H2O
(from solvent)
O
OH
OH
3a
(12%)
Pd/C
1a
2
4
O
A set of control experiments was also carried out for better
mechanistic understanding and to establish the role of Pd
metal (Scheme 2). The reaction of iodobenzene with maleic
acid was performed that yielded the corresponding product 3g
in 80% yield indicating that the first step will be hydrolysis of
maleic anhydride (Scheme 2, ‘a’). The reaction of 1g with
fumaric acid under standard reaction conditions afforded the
traces of product 3g (Scheme 2, ‘b’) and the reason may be
due to the non-fulfilment of the stereo-chemical and
electronic requirements of the reaction mechanism.12c To
investigate the role of base and Pd@PS catalyst, three
different reactions from expected intermediate 5 were carried
O
-
O
O
NR3Cl
Pd@ PS
NR3Cl
Pd@
PS
(II)
(I)
-
O
Ar-X
Pathway 'a'
Pathway 'b'
- CO2
Decompostion
at
polymer surface
O
-
Ar
Ar
O
-
NR3Cl
Pd@
X
PS
Pd@ PS
NR3Cl
O
O
X
-
O
(III)
(VI)
O
O
-
Ar
O
Ar
NR3Cl-
Pd@ PS
NR3Cl-
O
-
Pd@ PS
X
X
O
O
(IV)
K2CO3
(VII)
O
KX
O
O
O
O
NR3Cl-
NR3Cl-
Pd@ PS
X
Pd@
PS
Ar
O
Ar
(V)
2H+/H2O
O
COOH
(VIII)
Ar
3a
(80%)
H+/H2O
CO2
K2CO3
KX
(I)
Scheme 2. Set of Control Experiments
Scheme 3. Plausible Reaction Mechanism and Comparative Study with Pd/C
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The reaction of 1a with maleic anhydride in the presence of followed by migratory insertion to give intermediate (VIII).
Pd/C gave 3a only in 12% yield (Scheme 3 and Table 1, entry Then the reductive elimination of intermediate (VIII) gave the
18) which indicated partial decarboxylation of maleic desired cinnamic acid and also regenerating the Pd@PS
anhydride in solution phase.
catalyst (I) (Scheme 3, pathway ‘b’) for further reaction.
Based on the control experiments, the plausible reaction Considering all the results (Table 1, entry 18 and Scheme 2d),
mechanism comprises two reaction pathways. The maleic an- we assumed that the reaction is following major ‘Pathway a’
hydride undergoes hydrolysis (water present in PEG-400) to for this transformation and ‘Pathway b’ is the minor step for
give maleic acid which interacts with Pd@PS (I) generating the desired product synthesis. We propose that the cinnamic
intermediate (II). The pathway ‘a’ involves oxidative addition acid synthesis following this unprecedented approach could be
of aryl halides to intermediate (II) generating intermediate (III). a first report in this dimension.
Meanwhile, the subsequent interaction of maleic acid with Pd The developed methodology was further explored for its
metal centre gives intermediate (IV). The base helps in the substrate scope using different substituents at the aryl ring.
transmetallation step to form the intermediate (
intermediate ( ) is also supported by Scheme 2(c). The product 3b in 78% yield, while 2-iodotoluene gave 3c in
palladium assisted decarboxylation of the ( ) gave the desired comparatively low yield (71%) which may be attributed to the
V). The The reaction of 3-iodotoluene afforded the corresponding
V
V
cinnamic acids (Scheme 3). While as discussed earlier, in steric effect of the ortho substituent. The electron donating
Pathway “b” the interaction of Pd@PS with maleic acid may groups such as -OMe gave considerable yields (74-77%) of
assist its partial decarboxylation to acrylic acid giving rise to products 3d-e, while, 2-iodoanisole afforded 3f in 70% yield
initial intermediate (VI) from (II). The combined interaction of (Table 2). The reaction of iodobenzene and 1-iodonaphthalene
acrylic acid with Pd@PS afforded intermediate (VII) which is
gave the desired products 3g and 3h in 82 and 79% yields
respectively. The reaction was chemo-selective for different
halides (F, Cl and Br) on the phenyl ring affording the desired
Table 2. Pd@PS Catalyzed Synthesis of Cinnamic Acid Derivatives from Aryl Iodides and
Maleic Anhydride
products 3i, 3k-m in 78-86% yields (Table 2), while no
Pd@PS
[3 mol % of Pd]
K2CO3 (1equiv.)
dehalogenated product was detected in any case. The aryl
iodides having electron withdrawing substituents like -COCH3, -
CO2Me, -CF3, -CN, and -CHO also participated in reaction giving
the corresponding products 3n-r in considerably good yields
(Table 2). The O-protected aryl iodides also participated in the
reaction to give final products 3s and 3t in 76 and 75% yields
respectively (Table 2).
O
CO2H
CO2H
X
R
+
O
R
PEG-400:1,4-dioxane
125 oC, 12 h
2
3a-t
1a-t
CO2H
O
CO2H
H3CO
3b:
78%
CO2H
3c:
3f:
3d:
77%
71%
The aryl bromides were also targeted as substrates for the
same reaction. The aryl bromides containing electron donating
groups gave moderate yields of the corresponding products 3a
(64%) and 3g (61%); while the reaction with electron
withdrawing substrates on the aryl ring afforded the desired
CO2H
CO2H
e
OCH3
3e:
74%
OCH3
70%
3g
: 82%, 61%
CO2H
CO2H
CO2H
products 3i-j
The gram scale reaction of the aryl iodides was also attempted
using 4-iodotoluene as substrate. The reaction of with (3
, 3l and 3q-r in good yields (Table 2).
Cl
F
3j: 72%e
CO2H
b
e
Cl
3i:
3l:
85% , 74%
3h:
79%
1
2
CO2H
CO2H
equiv.) under the standard reaction conditions gave the
desired product 3a in good yield (Scheme 2). The NMR analysis
of the reaction mixture at 0.5 g scale after 6 h showed the
presence of fumaric, maleic and tolylmaleic acids. The
isomerization of maleic acid to unreactive fumaric acid may be
the reason that 3 equivalent of maleic anhydride is needed for
the conversion to desired product in considerably good yield.
Br
Br
F
b
e
b
86% , 71%
3k:
82%
3m:
78%)
CO2H
CO2H
CO2H
CO2H
H3COC
H3COOC
3o: 73%d
F3C
3n: 63%c
3p: 74%b
CO2H
CO2H
TsO
NC
OHC
3r:
Pd@PS
(2 mol% Pd)
O
3q: 71%b, 68%e
c
e
d
3s:
72% , 63%
76%
I
COOH
K2CO3 (1 equiv.)
+
O
CO2H
CO2H
PEG-400:1,4-dioxane
130 oC, 12h
Bn
O
1a
2
O
3a (70%)
e
3a:
3t: 75%
64%
Scheme 4. Gram Scale Reaction of 4-Iodotoluene
aReaction conditions: Aryl iodides 1 (1 equiv.), maleic anhydride 2 (3 equiv.),
K2CO3(1 equiv.), Pd@PS (3 mol% of Pd), 2 mL of PEG-400:1,4-dioxane (1:1) in a
closed tube; bfor 3i, 3k-l, 3p-q, t = 8-10h; cfor 3n and 3r, t = 20h; dfor 3o and 3s, t =
16 h; efor aryl bromides (1 equiv.), maleic anhydride (3 equiv.), K2CO3 (2 equiv.)
under aforementioned conditions at 130 oC; all yields refer to isolated yields.
The Hg poisoning experiment further established the
heterogeneity of Pd@PS catalyst as indicated by the low
product in 18% yield (ESI). Besides, the Pd@PS catalyst was
recycled upto five cycles without significant loss of catalytic
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Authors are grateful to Director CSIR-IHBT for providing
necessary facilities during the course of the work. The authors
thank CSIR, New Delhi for financial support as part of XII Five
Year Plan programme under title ORIGIN (CSC-0108) and
partial support from DST Nano Mission Project (SR/NM/NS-
1340/2014). VT and SK thank UGC-New Delhi for awarding
fellowships.
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,
3
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Catalysis Science & Technology
Page 6 of 6
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DOI: 10.1039/C7CY01126A
Polystyrene Supported Palladium Nanoparticles Catalyzed Cinnamic Acid
Synthesis using Maleic Anhydride as Substitute of Acrylic Acid
VandnaThakur,a,b,† Sandeep Kumar,a,b,† and Pralay Das*a,b
aNatural Product Chemistry and Process Development Division, CSIR-Institute of Himalayan Bioresource
Technology, Palampur-176061, (H. P.), India.
bAcademy of Scientific & Innovative Research, New Delhi, India.
†These authors contributed equally
.
Graphical Abstract:
Maleic anhydride as substitute of acrylic acid for cinnamic acids synthesis elaborating the combined role of support
and catalyst was explored.