S1
Polystyrene Supported Palladium Nanoparticles Catalyzed Cinnamic Acid
Synthesis using Maleic Anhydride as Substitute of Acrylic Acid
Vandna Thakur,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†equal contribution
CONTENTS
General Information …..……………………………………………………………….......S2
Preparation of Pd@PS catalyst............................…………………………………….........S2
Mechanistic investigation………………………………………………………………......S3-S6
Typical experimental procedures for synthesis of cinnamic acid derivatives and
Characterization data............................................................………………………………S7-S14
Recyclability Experiment......................................................................................................S14
TEM analysis of recycled Pd@PS catalyst………………………………………………...S15
ICP-AES analysis of the reaction mixture............................................................................S16
Mercury Test.........................................................................................................................S161H, 13C NMR spectra for the synthesized cinnamic acid derivatives……...........................S17-S36
References.............................................................................................................................S37
Electronic Supplementary Material (ESI) for Catalysis Science & Technology.This journal is © The Royal Society of Chemistry 2017
S2
1. General Information
High quality reagents and analytical grade solvents were purchased from Sigma Aldrich, TCI
Chemicals, Merck and Sd Fine Chem. Ltd. Amberlite® IRA 900 Cl− resin (PS) was procured
from Acros Organics. Reactions were monitored using TLC which was performed on pre coated
silica gel plates 60 F254 (purchased from Merck) in UV light detector. Silica gel (60-120 mesh
size) for column chromatography purchased from Merck was used for the purification of
compounds. 1H and 13C NMR spectra were recorded using a Bruker Avance 600 spectrometer
operating at 300/600 MHz (1H) and 75/150 MHz (13C) NMR spectra were recorded at 25 °C in
CD3OD [residual CH3OH (δH 3.33 and 4.86 ppm) and CH3OH (δc 49.00 ppm)], DMSO-d6
[residual DMSO (δH 2.50 and 3.42 ppm) and DMSO (δC 39.54 ppm)] with TMS as internal
standard. Chemical shifts were recorded in δ (ppm) relative to the TMS and NMR solvent signal,
coupling constants (J) are given in Hz and multiplicities of signals are reported as follows: s,
singlet; d, doublet; t, triplet; m, multiplet; br, broad singlet. Melting points were determined by
using MR-VIS+ melting point apparatus and are uncorrected.
2. Preparation of polystyrene supported Palladium (0) (Pd@PS) nanoparticles as catalyst
The solution of 30 mg NaBH4 in 10 mL distilled water was added to 1g of Amberlite® IRA 900
Cl− resin (PS) in 50 mL round bottom flask. The resulting mixture was stirred for 4 h at room
temperature. Then the partially borohydride exchanged resin was washed with water till the pH
became neutral and later with acetone to remove excess of water from polymer surface. This
exchanged polystyrene resin (PS-BH4‾ ) was dried under reduced pressure.
The PS-BH4- (1g) was added to the hot suspension of palladium acetate (10 mg) in DMF (10
mL) and the mixture was stirred for 1 h or till the brown colour solution changed to colourless
and PS-BH4‾ simultaneously turned black giving Pd@PS catalyst. After cooling, the Pd@PS
catalyst was filtered through cotton bed, washed with water and acetone and dried under reduced
pressure.
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3. Mechanistic investigationNMR investigation for intermediate and byproduct analysis
The reaction was performed under standard conditions using 1a (500 mg, 2.29 mmol), maleic
anhydride (673 mg, 6.87 mmol), K2CO3 (316 mg, 2.29 mmol) and Pd@PS (1028 mg, 2 mol% of
Pd) for 6h. The reaction residue after isolation of desired product was analysed by NMR studies
that clearly indicated the presence of maleic acid, fumaric acid and p-tolylmaleic acid.1H and 13C NMR spectra:
S4
200 180 160 140 120 100 80 60 40 20 0 ppm
21.02
39.12
39.26
39.40
39.54
39.67
39.81
39.95
115.69
126.77
129.85
130.38
130.67
134.16
140.51
148.82
166.18
166.23
166.93
169.14
Mechanistic investigation through FT-IR analysis:
We conducted the set of control experiments to establish the role of polymer support in the
reaction. We treated the polymer support (PS) with maleic anhydride and K2CO3 (same
equivalents as of standard reaction) under the optimized reaction conditions for 1 h. The PS was
filtered, washed with distilled water and acetone respectively and then dried under vacuum.
Further, PS was grinded into the fine powder and analyzed using FT-IR (Figure S1, ‘b’). Similar
experiment was performed using Pd@PS catalyst (Figure S1, ‘d’). All the recorded FT-IR
spectras including maleic acid (hydrolysed product of maleic anhydride) are summarized in
Figure S1 and S2.
The initial FT-IR spectra of PS and Pd@PS were found to be similar (Figure S1, ‘b’ and ‘d’).
The IR spectrum of PS after treatment with maleic anhydride under reaction conditions showed
the presence of new intense peaks in 1600-1200 cm-1 region (Figure S1, ‘c’). While, the
spectrum of Pd@PS (e) after treatment with maleic anhydride was also found similar to ‘c’
(Figure S1, ‘c’ and ‘e’).
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Figure S1. (a) FTIR spectra of Maleic acid; (b) FTIR spectra of polymer support (PS); (c) FTIR
spectra of PS after exchange with maleic anhydride for 1 h; (d) FTIR spectra of Pd@PS (e) FTIR
spectra of Pd@PS after exchange with maleic anhydride for 1 h.
S6
In another experiment, the Pd@PS-exchanged with maleic anhydride (as described above), was
subjected to the reaction with 4-iodotoluene under optimized conditions. The formation of
desired product 3a was observed. The Pd@PS recovered after the reaction was also subjected to
FT-IR analysis and the recorded IR spectra did not show the presence of intense peaks at 1581,
1356 and 1192 (Figure S2). This observation further proved the partial exchange of maleic acid
with polymer support hence facilitating the reaction at the polymer surface.
O
O
O
Pd@PS +K2CO3
125 oC,1 hPEG-400:Dioxane (1:1)
1). Pd@PS separated2). Washed3). Dried under vaccum
K2CO3
PEG-400:Dioxane125 oC
COOH
3a
1a
Figure S2. The FT-IR spectrum of Pd@PS after the reaction with 1a.
S7
4. Typical experimental procedures for synthesis of cinnamic acid derivatives from aryl
halides and characterization data:
(E)-3-p-tolylacrylic acid (3a)
4-iodotoluene 1a (100 mg, 0.459 mmol), maleic anhydride 2 (135 mg,
COOH
1.376 mmol), K2CO3 (63 mg, 0.459 mmol), and Pd@PS (309 mg, 3 mol % of Pd) were taken in
an oven dried screw capped reaction tube in 2 mL solvent mixture of PEG-400:Dioxane (1:1).
The resultant reaction mixture was stirred at 125 oC for 12 h. The progress of reaction was
monitored using TLC. The reaction mixture was cooled to ambient temperature and quenched
with water and then extracted using ethyl acetate (4 X 5 mL). The resulting organic layer was
treated with anhy. Na2SO4 and dried under reduced pressure. The corresponding (E)-3-p-
tolylacrylic acid 3a was obtained in 60 mg, 80% yield as white solid after purification by column
chromatography on silica gel (60-120 mesh) using Hexane:EtOAc (70:30) as elute; on the other
hand, 4-bromotoluene (100 mg, 0.585 mmol), maleic anhydride 2 (172 mg, 1.76 mmol), K2CO3
(161 mg, 1.169 mmol), and Pd@PS (394 mg, 3 mol% of Pd) under same reaction conditions at
130 oC, after column chromatography with Hexane:EtOAc (70:30), gave 3a as white solid (61
mg, 64%); mp 198-199 oC ( lit.1 mp 199-200 oC); 1H NMR (300 MHz, DMSO-d6) δ 2.31 (s,
3H), 6.45 (d, J = 15.99 Hz, 1H), 7.21 (d, J = 7.92 Hz, 2H), 7.51-7.57 (m, 3H); 13C NMR (75
MHz, DMSO-d6 ) δ 21.1, 118.1, 128.3, 129.6, 131.5, 140.3, 144.1, 167.8; IR (KBr) 2924, 2853,
1682, 1624, 1513, 1424 cm-1.
(E)-3-m-tolylacrylic acid (3b)
Prepared as described for 3a; 3-iodotoluene 1b (100 mg, 0.459 mmol) gave
COOH
3b, after purification with silica gel column chromatography (Hexane:EtOAc = 75:25) as white
solid (58 mg, 78%); mp 117-118 oC ( lit.2 mp 116-118 oC); 1H NMR (300 MHz, DMSO-d6) δ
2.31 (s, 3H), 6.50 (d, J = 15.9 Hz, 1H), 7.20-7.32 (m, 2H), 7.45- 7.57 (m, 3H); 13C NMR (75
MHz, DMSO-d6) δ 20.8, 119.0, 125.4, 128.6, 128.8, 130.9, 134.2, 138.2, 144.1, 167.6; IR (KBr)
2922, 2853, 1686, 1630, 1430 cm-1.
S8
(E)-3-o-tolylacrylic acid (3c)
Prepared as described for 3a; 2-iodotoluene 1c (100 mg, 0.459 mmol) gave
COOH
3c, after purification with silica gel column chromatography (Hexane:EtOAc = 70:30) as white
solid (53 mg, 71%); mp 174-176 oC ( lit.1 mp 175-176 oC); 1H NMR (300 MHz, DMSO-d6) δ
2.37 (s, 3H), 6.41 (d, J = 15.9 Hz, 1H), 7.20-7.32 (m, 3H), 7.69 (d, J = 7.2 Hz, 1H), 7.81 (d, J =
15.9 Hz, 1H); 13C NMR (75 MHz, DMSO-d6) δ 19.2, 128.2, 126.4, 126.5, 129.9, 130.7, 132.9,
137.1, 141.2, 167.5. IR (KBr) 2947, 2847, 1686, 1622, 1488, 1424 cm-1.
(E)-3-(4-methoxyphenyl)acrylic acid (3d)
Prepared as described for 3a; 4-iodoanisole 1d (100 mg, 0.427 mmol) H3CO
COOH
gave 3d, after purification with silica gel column chromatography (Hexane:EtOAc = 70:30) as
white solid (58 mg, 77%); mp 174-176 oC ( lit.1 mp 175-176 oC); 1H NMR (600 MHz, DMSO-
d6) δ 3.78 (s, 3H), 6.37 (d, J = 15.96 Hz, 1H), 6.96 (d, J = 8.28 Hz, 2H), 7.54 (d, J = 15.96 Hz,
1H), 7.62 (d, J = 8.28 Hz, 2H); 13C NMR (150 MHz, DMSO-d6) δ 55.3, 114.4, 116.5, 126.9,
129.9, 143.8, 161.0, 167.9; IR (KBr) 2972, 2938, 2843, 1684, 1623, 1513, 1432 cm-1.
(E)-3-(3-methoxyphenyl)acrylic acid (3e)
Prepared as described for 3a; 3-iodoanisole 1e (100 mg, 0.427 mmol) gave OCH3
COOH
3e, after purification with silica gel column chromatography (Hexane:EtOAc = 70:30) as white
solid (56 mg, 74%); mp 116-117 oC ( lit.2 mp 117-119 oC); 1H NMR (600 MHz, DMSO-d6) δ
3.78 (s, 3H), 6.54 (d, J = 15.96 Hz, 1H), 6.97-6.98 (dd, J1 = 8.15, J2 = 2.2 Hz, 1H), 7.23-7.25 (m,
2H), 7.32 (t, J = 7.8 Hz, 1H), 7.55 (d, J = 16.02 Hz, 1H); 13C NMR (150 MHz, DMSO-d6) δ
55.3, 112.9, 116.3, 119.6, 120.8, 129.9, 135.7, 143.9, 159.6, 167.6; IR (KBr) 2923, 2854, 1694,
1631, 1582, 1491, 1454, 1434 cm-1.
S9
(E)-3-(2-methoxyphenyl)acrylic acid (3f)
Prepared as described for 3a; 2-iodoanisole 1f (100 mg, 0.427 mmol) gave
COOH
OCH3
3f, after purification with silica gel column chromatography (Hexane:EtOAc = 70:30) as white
solid (53 mg, 70%); mp 182-183 oC ( lit.2 mp 182-184 oC); 1H NMR (600 MHz, DMSO-d6) δ
3.86 (s, 3H), 6.51 (d, J = 16.14 Hz, 1H), 6.98 (t, J = 7.5 Hz, 1H), 7.08 (d, J = 8.3 Hz, 1H), 7.39-
7.42 (m, 1H), 7.66-7.67 (dd, J1 = 7.68, J2 = 1.44 Hz, 1H), 7.84 (d, J = 16.2 Hz, 1H); 13C NMR
(150 MHz, DMSO-d6) δ 55.6, 111.7, 119.3, 120.8, 122.5, 128.4, 131.8, 138.8, 157.8, 167.9; IR
(KBr) 2974, 2946, 2842, 1683, 1620, 1490, 1463, 1427 cm-1.
Cinnamic acid (3g)
Prepared as described for 3a; iodobenzene 1g (100 mg, 0.49 mmol) gave 3g,
COOH
after purification with silica gel column chromatography (Hexane:EtOAc = 70:30) as white solid
(60 mg, 82%); also bromobenzene (100 mg, 0.637 mmol), maleic anhydride 2 (187 mg, 1.91
mmol), K2CO3 (176 mg, 1.27 mmol), and Pd@PS (429 mg, 3 mol% of Pd) under same reaction
conditions gave 3g, after purification with silica gel column chromatography (Hexane:EtOAc =
70:30) as white solid (58 mg, 61%); mp 132-134 oC ( lit.1 mp 133-134 oC); 1H NMR (600 MHz,
DMSO-d6) δ 6.531 (d, J = 15.6 Hz, 1H), 7.404-7.41 (m, 3H), 7.59 (d, J = 16.02 Hz, 1H), 7.67-
7.68 (m, 2H); 13C NMR (150 MHz, DMSO-d6) δ 119.2, 128.2, 128.9, 130.3, 134.3, 144.0, 167.6;
IR (KBr) 3024, 2924, 2854, 1691, 1631, 1453 cm-1.
(E)-3-(naphthalen-3-yl)acrylic acid (3h)
Prepared as described for 3a; 1-iodonaphthalene 1h (100 mg, 0.395 mmol)
COOH
gave 3h, after purification with silica gel column chromatography (Hexane:EtOAc = 75:25) as
white solid (62 mg, 79%); mp 212-213 oC ( lit.1 mp 213-214 oC); 1H NMR (600 MHz, DMSO-
d6) δ 6.60 (d, J = 15.72 Hz, 1H), 7.54-7.63 (m, 3H), 7.94 (d, J = 7.2 Hz, 1H), 7.97-8.01 (m, 2H),
8.19 (d, J = 8.4 Hz, 1H), 8.40 (d, J = 15.72 Hz, 1H); 13C NMR (150 MHz, DMSO-d6) δ 121.9,
S10
122.1, 125.2, 126.3, 127.2, 128.7, 130.4, 130.8, 131.0, 133.3, 140.2, 167.5; IR (KBr) 3048, 2971,
2836, 1682, 1619, 1511, 1424 cm-1.
(E)-3-(4-chlorophenyl)acrylic acid (3i)
Prepared as described for 3a; 1-chloro-4-iodobenzene 1i (100 mg, 0.419 Cl
COOH
mmol) gave 3i, after purification with silica gel column chromatography (Hexane:EtOAc =
65:35) as white solid (65 mg, 85%); also 1-bromo-4-chlorobenzene (100 mg, 0.523 mmol),
maleic anhydride 2 (154 mg, 1.57 mmol), K2CO3 (176 mg, 1.27 mmol), and Pd@PS (352 mg, 3
mol% of Pd) under same reaction conditions at 130 oC gave 3i, after purification with silica gel
column chromatography (Hexane:EtOAc = 65:35) as white solid (70 mg, 74%); mp 247-248 oC
( lit.2 mp 247-249 oC); 1H NMR (300 MHz, DMSO-d6) δ 6.54 (d, J = 16.05 Hz, 1H), 7.45 (d, J =
8.4 Hz, 2H), 7.57 (d, J = 16.02 Hz, 1H), 7.70 (d, J = 8.4 Hz, 2H); 13C NMR (75 MHz, DMSO-
d6) δ 120.1, 128.9, 129.9, 133.2, 134.7, 142.5, 167.4; IR (KBr) 2977, 2830, 1691, 1628, 1490,
1426 cm-1.
(E)-3-(3-chlorophenyl)acrylic acid (3j)
1-bromo-3-chlorobenzene 1j (100 mg, 0.523 mmol), maleic anhydride 2 (154
COOH
Cl
mg, 1.57 mmol), K2CO3 (176 mg, 1.27 mmol), and Pd@PS (352 mg, 3 mol% of Pd) under
aforementioned reaction conditions at 130 oC gave 3j, after purification with silica gel column
chromatography (Hexane:EtOAc = 75:25) as white solid (68 mg, 72%); mp 173-175 oC ( lit.3 mp
175-176 oC); 1H NMR (600 MHz, DMSO-d6) δ 6.60 (d, J = 16.02 Hz, 1H), 7.41-7.46 (m, 2H),
7.56 (d, J = 16.02 Hz, 1H), 7.65 (d, J = 7.32 Hz, 1H), 7.79 (s, 1H); 13C NMR (75 MHz, DMSO-
d6) δ 120.9, 126.7, 127.7, 129.7, 130.6, 133.7, 136.5, 142.2, 167.2; IR (KBr) 2992, 1696, 1630,
1570, 1480, 1430 cm-1.
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(E)-3-(4-bromophenyl)acrylic acid (3k)
Prepared as described for 3a; 1-bromo-4-iodobenzene 1k (100 mg, 0.35
COOH
Br
mmol) gave 3k, after purification with silica gel column chromatography (Hexane:EtOAc =
65:35) as white solid (65 mg, 82%); mp 251-253 oC ( lit.4 mp 253 oC); 1H NMR (600 MHz,
DMSO-d6) δ 6.56 (d, J = 16.02 Hz, 1H), 7.56 (d, J = 16.02 Hz, 1H), 7.60 (d, J = 8.52 Hz, 2H),
7.64 (d, J = 8.52 Hz, 2H); 13C NMR (150 MHz, DMSO-d6) δ 120.2, 123.6, 130.2, 131.9, 133.6,
142.7, 167.5; IR (KBr) 2978, 2835, 1689, 1626, 1485, 1425 cm-1.
(E)-3-(4-fluorophenyl)acrylic acid (3l)
Prepared as described for 3a; 1-fluoro-4-iodobenzene 1l (100 mg, 0.45
COOH
F
mmol) gave 3l, after purification with silica gel column chromatography (Hexane:EtOAc =
65:35) as white solid (64 mg, 86%); also 1-fluoro-4-bromobenzene (100 mg, 0.571 mmol),
maleic anhydride 2 (168 mg, 1.71 mmol), K2CO3 (158 mg, 1.14 mmol), and Pd@PS (385 mg, 3
mol% of Pd) under same reaction conditions gave 3l, after purification with silica gel column
chromatography (Hexane:EtOAc = 65:35) as white solid (67 mg, 71%); mp 209-210 oC ( lit.5 mp
209-211 oC); 1H NMR (600 MHz, DMSO-d6) δ 6.49 (d, J = 16.02 Hz, 1H), 7.23 (t, J = 8.7 Hz,
2H), 7.59 (d, J = 16.02 Hz, 1H), 7.74-7.76 (m, 2H); 13C NMR (150 MHz, DMSO-d6) δ 115.9 (d,
J = 21.69 Hz), 119.2, 130.5 (d, J = 8.60 Hz), 130.9 (d, J = 3.03 Hz), 142.7, 163.2 (d, J = 246.62
Hz), 167.6; IR (KBr) 2929, 2847, 1686, 1628, 1599, 1508, 1427 cm-1.
(E)-3-(4-bromo-2-fluorophenyl)acrylic acid (3m)
Prepared as described for 3a; 4-bromo-2-fluoro-1-iodobenzene 1m (100
COOH
FBr
mg, 0.332 mmol) gave 3m, after purification with silica gel column chromatography
(Hexane:EtOAc = 60:40) as white solid (63 mg, 78%); mp 218-219 oC; 1H NMR (600 MHz,
DMSO-d6) δ 6.60 (d, J = 16.14 Hz, 1H), 7.44-7.45 (dd, J1 = 8.4, J2 = 1.8 Hz, 1H), 7.57 (d, J =
16.2 Hz, 1H), 7.60 -7.62 (dd, J1 = 10.32 , J2 = 1.86 Hz, 1H), 7.77 ( t, J = 8.28 Hz, 1H); 13C NMR
(150 MHz, DMSO-d6) δ 119.5 (d, J = 25.15 Hz), 121.4 (d, J = 11.31 Hz), 122.6 (d, J = 5.38Hz),
123.8 (d, J = 9.95Hz), 128.3 (d, J = 3.21 Hz), 130.6 (d, J = 2.94 Hz), 134.7 (d, J = 2.83 Hz),
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160.2 (d, 254.38 Hz), 167.2; IR (KBr) 3069, 2926, 2852, 1692, 1625, 1599, 1565, 1482, 1415
cm-1.
(E)-3-(4-acetylphenyl)acrylic acid (3n)
Prepared as described for 3a; 4-iodoacetophenone 1n (100 mg, 0.40 H3COC
COOH
mmol) gave 3n, after purification with silica gel column chromatography (Hexane:EtOAc =
60:40) as white solid (48 mg, 63%); mp 223-225 oC ( lit.1 mp 224-226 oC); 1H NMR (600 MHz,
DMSO-d6) δ 2.59 (s, 3H), 6.67 (d, J = 16.2 Hz, 1H), 7.64 (d, J = 16.20 Hz, 1H), 7.83 (d, J = 8.4
Hz, 2H), 7.97 (d, J = 8.4 Hz, 2H); 13C NMR (150 MHz, DMSO-d6) δ 26.9, 121.8, 128.4, 128.7,
137.6, 138.6, 142.6, 167.3, 197.5; IR (KBr) 3343, 2960, 2922, 2852, 1682, 1630, 1603, 1563,
1424 cm-1.
(E)-3-(4-(methoxycarbonyl)phenyl)acrylic acid (3o)
Prepared as described for 3a; methyl 4-iodobenzoate 1o (100 mg,
COOH
H3COOC
0.382 mmol) gave 3o, after purification with silica gel column chromatography (Hexane:EtOAc
= 60:40) as white solid (57 mg, 73%); mp 245-246 oC ( lit.2 mp 245-247 oC); 1H NMR (600
MHz, DMSO-d6) δ 3.86 (s, 3H), 6.65 (d, J = 16.02 Hz, 1H), 7.63 (d, J = 16.02 Hz, 1H), 7.82 (d,
J = 8.4 Hz, 2H), 7.96 (d, J = 8.4 Hz, 1H); 13C NMR (150 MHz, DMSO-d6) δ 52.2, 121.9, 128.4,
129.6, 130.6, 138.8, 142.4, 165.7, 167.2; IR(KBr) 3414, 2955, 2846, 1712, 1686, 1631, 1567,
1429 cm-1.
(E)-3-(4-(trifluoromethyl)phenyl)acrylic acid (3p)
Prepared as described for 3a; methyl 1-(trifluoromethyl)-4-iodobenzene
COOH
F3C
1p (100 mg, 0.368 mmol) gave 3p, after purification with silica gel column chromatography
(Hexane:EtOAc = 60:40) as white solid (59 mg, 74%); mp 231-232 oC (lit.5 mp 231-233 oC); 1H
NMR (600 MHz, DMSO-d6) δ 6.67 (d, J = 16.02 Hz, 1H), 7.65 (d, J = 16.02 Hz, 1H), 7.75 (d, J
= 8.29 Hz, 2H), 7.91 (d, J = 8.16 Hz, 2H), 13C NMR (150/75 MHz, DMSO-d6) δ 122.2, 125.6 (q,
S13
J = 3.77 Hz), 128.7, 129.4, 129.8 (q, J = 31.70 Hz), 138.2, 141.9, 167.1; IR (KBr) 2990, 2841,
1696, 1632, 1581, 1427 cm-1.
(E)-3-(4-cyanophenyl)acrylic acid (3q)
Prepared as described for 3a; 4-iodobenzonitrile 1q (100 mg, 0.437 NC
COOH
mmol) gave 3q, after purification with silica gel column chromatography (Hexane:EtOAc =
60:40) as white solid (54 mg, 71%); also 4-bromobenzonitrile (100 mg, 0.549 mmol), ), maleic
anhydride 2 (161 mg, 1.65 mmol), K2CO3 (152 mg, 1.1 mmol), and Pd@PS (370 mg, 3 mol% of
Pd) under same reaction conditions at 130 oC gave 3q, after purification with silica gel column
chromatography (Hexane:EtOAc = 60:40) as white solid (65 mg, 68%) mp 253-255 oC ( lit.3 mp
254-255 oC); 1H NMR (300 MHz, DMSO-d6) δ 6.71 (d, J = 16.05Hz, 1H), 7.63 (d, J = 16.05 Hz,
1H), 7.85-7.91 (m, 4H); 13C NMR (75 MHz, DMSO-d6) δ 112.1, 118.5, 122.8, 128.8, 132.7,
138.8, 141.8, 167.1; IR (KBr) 2967, 2837, 2226, 1691, 1626, 1562, 1509, 1424 cm-1.
(E)-3-(4-formylphenyl)acrylic acid (3r)
Prepared as described for 3a; 4-iodobenzaldehyde (100 mg, 0.43
COOH
OHC
mmol) gave 3r, after purification with silica gel column chromatography (Hexane:EtOAc =
55:45) as white solid (54 mg, 72%); also 4-bromobenzaldehyde (100 mg, 0.540 mmol), ), maleic
anhydride 2 (159 mg, 1.62 mmol), K2CO3 (149 mg, 1.08 mmol), and Pd@PS (370 mg, 3 mol%
of Pd) under same reaction conditions at 130 oC gave 3r, after purification with silica gel column
chromatography (Hexane:EtOAc = 55:45) as white solid (60 mg, 63%); mp 250-252 oC; 1H
NMR (600 MHz, DMSO-d6) δ 6.70 (d, J = 16.08 Hz, 1H), 7.65 (d, J = 16.02 Hz, 1H), 7.90-7.94
(m, 4H), 10.02 (s, 1H); 13C NMR (150 MHz, DMSO-d6) δ 122.4, 128.8, 129.9, 136.8, 139.9,
142.4, 167.2, 192.7; IR (KBr) 2983, 2842, 1692, 1630, 1605, 1569, 1419 cm-1.
(E)-3-(4-(4-methylbenzenesulfonoyl)phenyl)acrylic acid (3s)
Prepared as described for 3a; 4-iodophenyl 4-methylbenzenesulfonate
COOH
TsO
1s (100 mg, 0.267 mmol) gave 3s, after purification with silica gel column chromatography
S14
(Hexane:EtOAc = 65:35) as white solid (65 mg, 76%); mp 202-203 oC ( lit.6 mp 201-202 oC); 1H
NMR (600 MHz, CD3OD) δ 2.44 (s, 3H), 6.43 (d, J = 15.96 Hz, 1H), 7.01 (d, J = 8.58 Hz, 2H),
7.41 (d, J = 8.1 Hz, 2H), 7.55 (d, J = 8.58 Hz, 2H), 7.60 (d, J = 16.02 Hz, 1H), 7.69 (d, J = 8.16
Hz, 2H); 13C NMR (150 MHz, CD3OD) δ 20.6, 119.7, 122.9, 128.6, 129.5, 130.1, 132.5, 134.0,
143.4, 146.4, 151.2, 168.9; IR (KBr) 2978, 1688, 1631, 1596, 1504, 1428 cm-1.
(E)-3-(4-(benzyloxy)phenyl)acrylic acid (3t)
Prepared as described for 3a; 1-((4-iodophenoxy)methyl)benzene 1t
COOH
BnO
(100 mg, 0.32 mmol) gave 3t, after purification with silica gel column chromatography
(Hexane:EtOAc = 65:35) as white solid (61 mg, 75%); mp 208-210 oC ( lit.7 mp 209-211 oC); 1H
NMR (600 MHz, DMSO-d6) δ 5.15 (s, 2H), 6.38 (d, J = 15.96 Hz, 1H), 7.04 (d, J = 8.76 Hz,
2H), 7.33 (t, J = 7.26 Hz, 1H), 7.39 (t, J =7.5 Hz, 2H), 7.45 (d, J = 7.26 Hz, 2H), 7.54 (d, J =
15.96 Hz, 1H), 7.63 (d, J = 8.76 Hz, 2H); 13C NMR (150 MHz, DMSO-d6) δ 69.3, 115.2, 116.6,
127.0, 127.7, 127.9, 128.5, 129.9, 136.7, 143.7, 160.0, 167.8; IR (KBr) 3031, 2930, 2836, 1668,
1601, 1512, 1430 cm-1.
5. Typical experimental procedure for reaction of 4-iodotoluene in gram scale:
For gram scale reaction, 4-iodotoluene 1a (1 g, 4.58 mmol), maleic anhydride (1.35 g, 13.76
mmol), K2CO3 (633 mg, 4.48 mmol) and Pd@PS (2059 g, 2 mol% of Pd) were treated under the
aforementioned conditions to give 3a after purification with silica gel column chromatography
(Hexane:EtOAc = 70:30) as final product (520 mg, 70%).
6. Recyclability Experiments
The recyclability experiment of Pd@PS was carried out using 4-iodotoluene as model substrate
under the optimum reaction conditions. The catalyst was recovered, washed with water and then
with acetone, dried under reduced pressure after each cycle before applying it in the next
reaction. The catalyst was successfully applied upto 5th cycle as the isolated yield of product 3a
showed less decrease upto 5th cycle.
S15
Cycles Yield 3a (%)
1 80
2 80
3 77
4 75
5 69
7. TEM analysis of Pd@PS after 5th cycle:
TEM analysis of Pd@PS after recyclability experiments was performed to find outs the size and
dispersion of Pd NPs. The TEM image at 50 nm showed the presence of Pd NPs and the
corresponding particle size distribution histogram confirmed the average number of NPs having
size in range of 1-3 nm. The study reveals that the size of nanoparticles of Pd@PS remains
unaffected after 5th cycle of reaction. But, NPs were not well dispersed as of fresh Pd@PS
catalyst. The nanoparticles clustering might be the reason for loss of catalytic activity.
Figure S3. (a) TEM at 50 nm (b) Particle size distribution histogram from (a)
S16
8. ICP-AES studies
ICP-AES analysis was performed for the reaction mixture using 4-iodotoluene as model
substrate under standard reaction conditions. The reaction mixture after complete digestion under
acidic conditions was subjected for ICP-AES analysis which showed leaching less than 1 ppm.
9. Mercury Test
The reaction of 4-iodotoluene under standard reaction conditions was screened for mercury test.
We conducted the test using 500 equiv. of Hg(0) with respect to Pd@PS (3 mol% of Pd).
Initially we stirred the Hg(0) and Pd@PS catalyst for half an hour followed by the addition of 4-
iodotoluene (1 equiv.), maleic anhydride (3 equiv.) and K2CO3 (1 equiv.) in PEG-400:Dioxane
(1:1) and reaction was performed under optimized reaction conditions. The product 3a was
isolated in 18% yield indicating the poisoning of catalyst.
S17
10. NMR (1H and 13C) Spectra
(E)-3-p-tolylacrylic acid (3a)
190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
21.09
38.66
38.94
39.22
39.50
39.78
40.05
40.33
118.13
128.27
129.64
131.55
140.32
144.08
167.81
3a
COOH
1H NMR, (300 MHz, ((CD3)2SO)
COOH
3a13C NMR (75 MHz (CD3)2SO)
S18
(E)-3-m-tolylacrylic acid (3b)
190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
20.86
20.88
38.72
39.00
39.28
39.56
39.83
40.11
40.39
119.04
125.46
128.68
128.83
130.97
134.20
138.20
144.09
167.62
COOH
3b
13C NMR (75 MHz (CD3)2SO)
COOH
3b
1H NMR (300 MHz (CD3)2SO)
S19
(E)-3-o-tolylacrylic acid (3c)
-10190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
19.2
4
38.6
838
.95
39.2
339
.51
39.7
940
.07
40.3
4
120.
1812
6.40
126.
4612
9.93
130.
6813
2.90
137.
1214
1.15
167.
50
COOH
3c1H NMR (300 MHz (CD3)2SO)
COOH
3c13C NMR (75 MHz (CD3)2SO)
S20
(E)-3-(4-methoxyphenyl)acrylic acid (3d)
11 10 9 8 7 6 5 4 3 2 1 ppm3.419
3.780
6.359
6.386
6.951
6.965
7.530
7.556
7.618
7.632
3.06
1.00
1.99
1.00
2.03
190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
39.10
39.24
39.38
39.52
39.66
39.80
39.94
55.34
114.40
116.55
126.88
129.99
143.81
161.00
167.91
COOH
3dH3CO
1H NMR (600 MHz (CD3)2SO)
COOH
3dH3CO
13C NMR (150 MHz (CD3)2SO)
S21
(E)-3-(3-methoxyphenyl)acrylic acid (3e)
9 8 7 6 5 4 3 2 1 0 ppm
2.50
2.50
2.50
3.41
3.78
6.53
6.56
6.97
6.97
6.98
6.98
7.23
7.25
7.25
7.31
7.32
7.33
7.54
7.57
3.02
1.00
1.00
2.03
1.01
1.00
200 180 160 140 120 100 80 60 40 20 0 ppm
39.10
39.24
39.38
39.52
39.66
39.80
39.93
55.27
112.95
116.32
119.61
120.81
130.00
135.70
143.94
159.65
167.64
OCH3
COOH
3e1H NMR (600 MHz (CD3)2SO)
OCH3
COOH
3e13C NMR (150 MHz (CD3)2SO)
S22
(E)-3-(2-methoxyphenyl)acrylic acid (3f)
9 8 7 6 5 4 3 2 1 0 ppm
1.98
2.08
3.86
6.50
6.52
6.97
6.98
6.99
7.07
7.09
7.39
7.39
7.40
7.41
7.42
7.66
7.66
7.67
7.67
7.83
7.85
3.05
1.00
1.00
1.01
1.00
1.01
1.00
200 180 160 140 120 100 80 60 40 20 0 ppm
39.10
39.24
39.38
39.52
39.66
39.80
39.93
55.67
111.76
119.31
120.77
122.52
128.46
131.82
138.77
157.78
167.92
COOH
OCH33f
1H NMR (600 MHz (CD3)2SO)
COOH
OCH33f
13C NMR (150 MHz (CD3)2SO)
S23
Cinnamic acid (3g)
11 10 9 8 7 6 5 4 3 2 1 0 ppm
2.49
9
3.43
0
6.51
76.
544
7.40
37.
407
7.41
37.
577
7.60
37.
670
7.67
37.
679
7.68
57.
731
1.00
3.01
1.02
2.09
-10190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
39.1
039
.24
39.3
839
.52
39.6
639
.80
39.9
4
119.
27
128.
2712
8.99
130.
3113
4.28
144.
03
167.
67
COOH
3g1H NMR, (600 MHz, (CD3)2SO)
COOH
3g13C NMR (150 MHz (CD3)2SO)
S24
(E)-3-(naphthalen-3-yl)acrylic acid (3h)
190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
39.09
39.23
39.37
39.50
39.64
39.78
39.92
121.93
123.00
125.26
125.76
126.32
127.17
128.75
130.41
130.78
131.02
133.33
140.23
167.48
COOH
3h1H NMR, (600 MHz, (CD3)2SO)
COOH
3h13C NMR (150 MHz (CD3)2SO)
S25
(E)-3-(4-chlorophenyl)acrylic acid (3i)
190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
38.67
38.95
39.22
39.50
39.78
40.06
40.34
120.09
128.93
129.89
133.22
134.74
142.51
167.42
Cl
COOH
3i13C NMR (75 MHz, (CD3)2SO)
Cl
COOH
3i1H NMR (300 MHz (CD3)2SO)
S26
(E)-3-(3-chlorophenyl)acrylic acid (3j)
11 10 9 8 7 6 5 4 3 2 1 ppm
2.496
2.499
2.501
3.436
6.591
6.618
7.412
7.425
7.438
7.445
7.448
7.456
7.459
7.547
7.574
7.644
7.656
7.789
1.01
2.00
1.01
1.01
1.00
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 ppm
38.68
38.96
39.23
39.51
39.79
40.07
40.35
120.98
126.69
127.73
129.75
130.64
133.72
136.51
142.23
167.25
Cl
OH
O
3j1H NMR (600 MHz (CD3)2SO)
Cl
OH
O
3j13C NMR (150 MHz (CD3)2SO)
S27
(E)-3-(4-bromophenyl)acrylic acid (3k)
190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
39.10
39.23
39.37
39.51
39.65
39.79
39.93
120.17
123.58
130.20
131.90
133.57
142.67
167.48
Br
COOH
3k13C NMR (150 MHz, (CD3)2SO)
Br
COOH
3k1H NMR (600 MHz (CD3)2SO)
S28
(E)-3-(4-fluorophenyl)acrylic acid (3l)
11 10 9 8 7 6 5 4 3 2 1 ppm
2.499
6.473
6.500
7.214
7.229
7.243
7.572
7.599
7.735
7.745
7.749
7.758
1.00
2.01
1.00
2.06
190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
39.10
39.24
39.38
39.52
39.66
39.80
39.93
115.84
115.98
119.16
130.50
130.55
130.93
130.95
142.73
162.37
164.02
167.57
F
COOH
3l13C NMR (150 MHz (CD3)2SO)
F
COOH
3l1H NMR (600 MHz (CD3)2SO)
S29
(E)-3-(4-bromo-2-fluorophenyl)acrylic acid (3m)
9 8 7 6 5 4 3 2 1 0 ppm
2.50
2.50
2.50
3.46
6.58
6.61
7.44
7.44
7.45
7.45
7.55
7.58
7.60
7.60
7.61
7.62
7.76
7.77
7.78
1.00
1.00
0.99
1.01
1.01
200 180 160 140 120 100 80 60 40 20 0 ppm
39.10
39.24
39.38
39.52
39.66
39.80
39.93
119.45
119.62
121.37
121.44
122.59
122.63
123.81
123.88
128.26
128.29
130.65
130.67
134.72
134.74
159.39
161.08
167.21
O
OH
F
Br3m
1H NMR (600 MHz, (CD3)2SO)
3m
O
OH
F
Br3m
13C NMR (150 MHz, (CD3)2SO)
S30
(E)-3-(4-acetylphenyl)acrylic acid (3n)
200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
26.87
39.10
39.24
39.38
39.52
39.66
39.80
39.93
121.81
128.44
128.71
137.60
138.61
142.61
167.33
197.55
H3COC
COOH
3n13C NMR (150 MHz, (CD3)2SO)
H3COC
COOH
3n1H NMR (600 MHz, (CD3)2SO)
S31
(E)-3-(4-(methoxycarbonyl)phenyl)acrylic acid (3o)
11 10 9 8 7 6 5 4 3 2 1 ppm
2.496
2.499
2.502
3.378
3.389
3.857
6.635
6.662
7.616
7.643
7.814
7.828
7.953
7.967
2.98
1.00
1.00
2.01
2.05
190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
39.10
39.24
39.38
39.52
39.66
39.80
39.94
52.27
121.98
128.40
129.59
130.58
138.78
142.38
165.78
167.24
H3COOC
COOH
3o13C NMR (150 MHz, (CD3)2SO)
H3COOC
COOH
3o1H NMR, (600 MHz, (CD3)2SO)
S32
(E)-3-(4-(trifluoromethyl)phenyl)acrylic acid (3p)
190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
38.68
38.96
39.24
39.52
39.80
40.07
40.35
122.21
125.53
125.58
125.63
125.68
125.77
128.73
129.14
129.38
129.57
129.99
130.41
138.25
141.90
167.07
F3C
COOH
3p13C NMR (150 MHz, (CD3)2SO)
F3C
COOH
3p13C NMR (600 MHz, (CD3)2SO)
S33
(E)-3-(4-cyanophenyl)acrylic acid (3q)
190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
38.68
38.96
39.24
39.52
39.80
40.07
40.35
112.08
118.55
122.83
128.83
132.68
138.82
141.85
167.06
NC
COOH
3q13C NMR (75 MHz, (CD3)2SO)
NC
COOH
3q1H NMR (300 MHz (CD3)2SO)
S34
(E)-3-(4-formylphenyl)acrylic acid (3r)
11 10 9 8 7 6 5 4 3 2 1 ppm
2.500
3.369
6.681
6.708
7.640
7.667
7.898
7.912
7.921
7.935
10.021
190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
39.58
39.72
39.86
39.99
40.13
40.27
40.41
122.91
129.25
130.34
137.31
140.36
142.86
167.66
193.10
OHC
COOH
3r13C NMR, (150 MHz, (CD3)2SO)
OHC
COOH
3r1H NMR (600 MHz, (CD3)2SO)
S35
(E)-3-(4-(4-methylbenzenesulfonoyl)phenyl)acrylic acid (3s)
11 10 9 8 7 6 5 4 3 2 1 ppm
2.435
3.300
4.865
6.421
6.447
7.004
7.019
7.398
7.411
7.543
7.557
7.585
7.611
7.684
7.698
3.06
1.00
2.00
1.96
2.00
1.11
2.07
190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
21.76
48.72
48.86
49.00
49.14
49.28
49.43
49.57
120.82
124.10
129.79
130.69
131.24
133.64
135.16
144.56
147.55
152.34
170.09
TsO
COOH
3s13C NMR (150 MHz, (CD3OD)
TsO
COOH
3s1H NMR (600 MHz, (CD3OD)
S36
(E)-3-(4-(benzyloxy)phenyl)acrylic acid (3t)
11 10 9 8 7 6 5 4 3 2 1 ppm
2.499
3.401
5.145
6.364
6.391
7.032
7.047
7.329
7.341
7.377
7.389
7.402
7.440
7.452
7.528
7.555
7.621
7.635
2.03
1.00
1.98
0.99
2.01
2.00
1.00
2.00
190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm
39.09
39.23
39.37
39.51
39.64
39.78
39.92
69.36
115.22
116.65
127.05
127.75
127.95
128.49
129.95
136.75
143.71
160.03
167.85
BnO
COOH
3t13C NMR, (150 MHz, (CD3)2SO)
BnO
COOH
3t1H NMR (600 MHz, (CD3)2SO)
S37
References:
1) Fukuyama, T.; Arai, M.; Matsubara, H.; Ryu I. J. Org. Chem. 2004, 69, 8105-8107.
2) Pardin, C.; Pelletier, J. N.; Lubell, W. D.; Keillor, J. W. J. Org. Chem. 2008, 73, 5766-
5775.
3) Pawar, P. M.; Jarag K. J.; Shankarling, G. S. Green Chem., 2011, 13, 2130-2134.
4) Ghorai, P.; Kraus, A.; Keller, M.; Go¨tte, C.; Igel, P.; Schneider, E.; Schnell, D.;
Bernhardt, G.; Dove, S.; Zabel, M.; Elz, S.; Seifert, R.; Buschauer A. J. Med. Chem.,
2008, 51, 7193-720.
5) Shil, A. K.; Kumar, S.; Reddy, C. B.; Dadhwal, S.; Thakur, V.; Das P. Org. Lett., 2015,
17, 5352-5355
6) Dale, W. J.; Hennis, H. E.; J. Am. Chem. Soc., 1956, 78, 2543-2547.
7) Doherty, D. G.; J. Am. Chem. Soc., 1955, 77, 4887-4892.
8)