Polymeric β-alanine incarcerated Pd(ii) catalyzed allylic etherification in water: A mild and efficient method for the formation of C(sp3)-O bonds

Article abstract of DOI:10.1039/c5ra26182a

A new heterogeneous palladium(ii) catalyst has been developed through a convenient and economic way. The catalyst was synthesized by confining palladium metal with a polystyrenal β-alanine-imine network and characterized by FT-IR spectroscopy, thermogravimetric analysis, field emission scanning electron microscopy, energy dispersive X-ray, and elemental analysis. Polymeric imine can be prepared easily from chloromethylated polystyrene and β-alanine. Using this polymer incarcerated palladium(ii) catalyst a useful and efficient procedure for stereospecific synthesis of allyl-aryl ethers has been developed. The benzylic, aromatic, and heteroaromatic phenols react with various substituted allyl acetates by this procedure to furnish a library of allyl-aryl and allyl-hetero-aryl ethers in high yields. The catalyst could be recovered easily and reused five times without any considerable loss of its catalytic activity.

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Polymeric
β
-alanine incarcerated Pd(II) catalyzed allylic
etherification in water: A mild and efficient method for the
formation of C(sp3)-O bond
Received 00th January 20xx,
Accepted 00th January 20xx
Mita Halder,a,b Md. Mominul Islam,b Sabir Ahammed,c,* Sk. Manirul Islam b,*
DOI: 10.1039/x0xx00000x
A new heterogeneous palladium(II) catalyst has been developed through a convenient and economic way. The catalyst was
synthesized by confining palladium metal with polystyrenal β-alanine-imine network and characterized by FT-IR
spectroscopy, thermogravimetric analysis, field emission scanning electron microscopy, energy dispersive X-ray, and
elemental analysis. Polymeric imine can be prepared easily from chloromethylated polystyrene and β-alanine. Using this
polymer incarcerated palladium (II) catalyst a useful and efficient procedure for stereospecific synthesis of allyl-aryl ether
has been developed. The benzylic, aromatic, and heteroaromatic phenols react with various substituted allyl acetates by
this procedure to furnish a library of allyl-aryl and allyl-hetero-aryl ethers in high yields. The catalyst could be recovered
www.rsc.org/
easily
and
reused
five
times
without
any
considerable
loss
of
its
catalytic
activity.
highly active Pd(II) catalyst and exemplified its application for the
stereo-specific allylic etherification reactions in water under mild
condition. The catalyst was prepared easily by two step reaction.
The initial step is the formation of polymeric imine by the
condensation of chloromethylated polystyrene with readily
Introduction
Homogeneous palladium complexes have been used successfully
for a variety of reactions in organic synthesis.1 But due to the
chance of metal contamination with the end product and the
difficulty to recover and reuse the homogeneous catalyst,
heterogeneous Pd catalyst has emerged as sustainable alternative.
Thus the immobilization of palladium on a heterogeneous support
has received considerable attention to provide an effective catalyst
overcoming the drawbacks of homogeneous catalysis.2
Furthermore, the use of water as the reaction medium has gained
top priority because of its unique reactivity and selectivity which is
different from those in organic solvents, in addition to its
environmental acceptability and low cost.3 Thus, the combination of
heterogeneous, inexpensive, ligand-free, robust, recyclable
catalysts and water as a solvent for a chemical transformation is
highly desirable in the context of environmental and industrial
concerns. Recently, polymer-supported phosphine and amine ligand
have been developed to immobilize palladium metals onto
polymers.4 Our group has explored few polymer supported metal
catalyst for hydrogenation,5 C-C and C-N cross coupling reaction6
and catalytic oxidation.7 We report here a simple preparation and
available and inexpensive β-alanine. Finally the PS-Pd-ala catalyst
was prepared by the immobilizing the palladium metal on polymeric
imine, for the first time.
The construction of C(sp3)-O bond is very important in organic
synthesis as it constitutes the key step in the synthesis of many
pharmaceuticals.8 Allyl ethers are employed as useful starting
material in a wide variety of reactions such as 1,3-hydrogen shift,
[3,3]-sigmatropic rearrangement, and polymerization reactions.9
They are also found as core units of several biologically active
molecules and natural products.10 In addition, allyl groups act as
efficient protecting groups for phenol derivatives.11 Usually
allylation is performed using allyl alcohol derivatives or halides.12
But, easy availability and configurational stability of allyl acetate
make it preferable allylating agents compared to highly activated,
unstable allyl halides and tosylates.13 Transition metal-catalyzed
allylation of carbon, nitrogen and sulfur nucleophile is one of the
most frequently employed transformations in organic synthesis.14-17
Generally, allyl ethers are prepared by the reaction between alkyl
halide and phenols using strong base e,g metal alkoxide.18 However,
allylation with soft phenolic nucleophile has received less attention.
Few transition metal complexes such as Pd,19 Ru,20 Ir,21 Ni22 have
been explored as the catalysts for the synthesis of allyl ethers. In
fact, majority of the methods involved non recyclable, costly
homogeneous transition metal catalyst. Therefore an alternative
sustainable heterogeneous catalyst is highly desirable for the
synthesis of allyl ether. Verma et al reported a mild procedure for
the general O-allylation of phenols with allyl acetates using
characterization of a new polymeric β-alanine-imine incarcerated
a.Department of Chemistry, University of Calcutta, Kolkata- 700009, W.B., India
b.Department of Chemistry, University of Kalyani, Kalyani, Nadia, 741235, WB,
India, Tel.: +91 33 2582 8750; Fax: +91 33 2582 8282, E-mail:
manir65@rediffmail.com
c. Department of Chemistry, Aliah University, IIA/27 New Town, Kolkata-700156,
WB, India, Tel: +91 33 2473 4971, E-mail: sabir.ju@gmail.com
Electronic Supplementary Information (ESI) available: Copies of 1H NMR and 13C
NMR spectra of all products listed in Tables 2, Scheme 3,
DOI: 10.1039/x0xx00000x
4 and 5. See
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magnetically separable heterogeneous Pd catalyst.23 Here we The reaction failed to initiate at room temperature and these are
report the application of our catalyst for a mild and efficient allylic then carried out under refluxing condition. There was no reaction in
C(sp3)-O bond formation (Scheme 1).
the absence of supported Pd(II) catalyst (Table 1, entry 15). The
yield of the product (3c) was not affected after the addition of 1
equiv. of TEMPO (Table 1, entry 16). Best yield was obtained using
H2O as a solvent and 10 mol% Pd(II) catalyst in presence of K2CO3
under reflux for 16 h (argon atmosphere) (Table 1, entry 8). In our
preliminary screening, it was exciting to demonstrate that polymer
incarcerated Pd(II) catalyst was slightly more reactive than the
homogeneous Pd(II) acetate catalyst (Table 1, entry 17).
Pd(II) cat., K2CO3
R2
R1
OAc +
R
R1
O
2
OH
H2O, reflux, 16 h
Scheme 1 Palladium catalyzed allylic etherification
Results and discussion
2.1 Allylic etherification
Both aliphatic and aromatic allyl acetates were found to be
efficient substrates for the O-allylation reaction. The allyl acetate
bearing phenyl with an electron-donating group at para- position
To probe the optimum reaction conditions, a series of experiments
were performed with variation of reaction parameters such as base,
solvent, temperature and time for a representative O-allylation of
cinnamyl acetate (1b) with p-cresol (2b). The results are
summarized in Table 1. Water was found to be best solvent among
THF, DMF, toluene, 1,4-dioxane, CH3CN, NMP and DMSO tried for
this reaction. Among various bases K2CO3 was found more effective
than Cs2CO3 and K3PO4 under identical condition. NaHCO3 shows
almost similar activity compared to K2CO3.
Table 2 Synthesis of allyl aryl ether using Pd catalysta
O
Table 1 Standardization of reaction conditionsa
O
O
Me
3b, 85%
3a, 81%
OMe
Me
O
O
3d, 88%
Yielda
(%)
3c, 90%
Entry
1
Solvent
Base
Temp.
(oC)
Time
(h)
Me
O
O
THF
K2CO3
70
16
39
O
3e, 84%
MeO
3f, 81%
2
3
4
DMF
K2CO3
K2CO3
K2CO3
110
110
105
16
16
16
62
18
43
F
Toluene
Dioxane
O
O
OMe
3h, 86%
3g, 89%
Br
OH
5
6
MeCN
NMP
DMSO
H2O
K2CO3
K2CO3
K2CO3
K2CO3
K3PO4
Cs2CO3
NaHCO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
80
16
16
16
16
16
16
16
30
30
20
12
16
16
16
38
44
90
42
37
85
91
-
O
O
110
110
100
100
100
100
100
rt
3j, 82%
3i, 89%
7
O
CN
O
O
O
8
3k, 89%
3l, 86%
Br
9
H2O
O
N
O
10
11
12
13
14
15b
16c
17d
H2O
Me
MeO
Br
3m, 84%
3n, 90%
H2O
Br
Me
Br
H2O
O
O
3p, 84%
3o, 94%
MeO
Me
H2O
Me
H2O
70
83
-
O
O
H2O
100
100
100
3r, 81%
3q, 89%
O
Me
H2O
88
O
H2O
76
O
OMe
aYields refer to those of purified products characterized by 1H and 13C NMR
spectroscopic data. bWithout using catalyst. cIn presence of TEMPO.dPalladium(II)
acetate was used as a catalyst.
3t, 91%
3s, 92%
aYields refer to those of purified products characterized by 1H and 13C NMR
spetroscopic data
2 | J. Name., 2012, 00, 1-3
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formed the product in good yield and the reactions are more facile
than those with unsubstituted one. Significantly, the reaction is
uniform with ortho- and para-substituted cinnamyl acetates. The O-
allylation of (E)-3-(4-bromophenyl)allyl acetate is highly
chemoselective as the attack of nucleophile occurs only at allylic
position leaving -Br group on the aromatic ring unaffected (Table 2,
3r).24 A series of diversely substituted phenols underwent reactions
with substituted allyl acetates by this procedure to provide the
corresponding allyl-aryl ethers. The phenols bearing various
electron donating (-Me, -OMe,) and withdrawing moieties (-F, -
COMe) at the different positions of the aromatic ring underwent
coupling with allyl and cinnamyl acetates without any difficulty
(Table 2). With an ortho-2,6-dimethoxy-substituted phenol, the
cinnamyl acetate (1b) gave a reasonable yield of the allylation
product, although the nucleophile is more sterically hindered (Table
2, 3g). It was found that the reactivity of hydroxy groups attached
with aromatic system is greater than aliphatic one. We performed
the reaction of cinnamyl acetate with 4-(hydroxymethyl)phenol and
(4-(cinnamyloxy)phenyl)methanol was obtained as the single
product (Table 2, 3j). We also investigated the reactions of several
heterocyclic phenols with allyl and cinnamyl acetates and the
coupling reaction occurs without any difficulty (Table 2, 3l and 3m).
Scheme 4 O-Allylation using branched cinnamyl acetate.
We suggest that the reaction proceeds through an interaction of
Pd(II) with allyl acetate followed by oxidative addition with
substituted phenol resulting a η3-π-allyl complex, which undergoes
reductive elimination to give the product (Scheme 5).17a In case of
trans-allyl acetate, it is predicted that the direct interaction of π-
allyl complex [A] with phenol, followed by reductive elimination
gives the trans product. However in case of cis-allyl acetate, the
intermediate [B], formed after the oxidative addition, is likely to
equilibrate with stable, less congested intermediate [A] and finally
gives the trans product.
Significantly, the (E)- cinnamyl acetates and substituted phenol
produced the corresponding (E)- allyl aryl ether with complete
retention of stereochemistry. Interestingly, the (Z)- cinnamyl
acetates also provided (E) products with excellent stereospecificity
(Scheme 2)
Scheme 5 Plausible mechanism.
Experimental
3.1 Loading of metal ions on to the polymeric ligand
Scheme 2 Synthesis of (E)-allyl-aryl ether using (Z)-cinnamyl acetate.
Polymeric ligand (3) (1 gm) was stirred for 20 h with palladium
o
acetate (20 mg) in acetic acid (10 mL) at 100 C (Scheme 6). At the
Substituted benzyl alcohols also coupled with cinnamyl acetate
successfully to produce the corresponding ethers (Scheme 3, 5a). In
this reaction we have used strong base like NaOH instead of K2CO3
for the completion of reaction.
end of the reaction, the resulting metal-loaded polymer was
filtered, washed with water, followed by methanol and finally dried
under vacuum for 6 h at 90 oC.
Scheme 3 Synthesis of benzyl-allyl ether using benzyl alcohol.
In case of branched allyl acetate (Scheme 4, 3c, 3u), this reaction
shows equal efficiency to provide linear allyl-aryl ether which also
supports the mechanism that entails the intermediacy of an η3-π-
allyl Pd complex as the key intermediate in the reaction (Scheme 5).
Scheme 6 Outline for the synthesis of polymer incarcerated palladium(II) catalyst
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3.2 Characterization of supported palladium(II) complex
3.2.2 DRS-UV study
The electronic spectrum (Figure 2) of the polymer supported Schiff
base ligand and palladium catalyst (Pd-PS-ala) have been recorded
in the diffuse reflectance spectrum mode as MgCO3/BaSO4 disc due
to its solubility limitations in common organic solvents. In the
catalyst, broad bands around 260 to 350 nm are observed. This
absorption bands may be attributed to π→π* and n→π* transiꢀon
in phenyl moiety. The bands at 390-430 nm arise due to LMCT.
Due to insolubility of the polymer supported Pd(II) complex in all
common organic solvents, characterization was limited to the
physicochemical properties, chemical analysis, SEM, TGA, IR, and
UV-Vis spectral data. Elemental analysis data for polymer supported
ligand and catalyst are tabulated in Table 3. Amount of metal was
determined by stripping the bound metal from the support and
analysis by using atomic absorption spectrophotometer. Palladium
content was found in the catalyst is 10.34 wt% of Pd analyzed by
AAS (Table 3). Palladium content remained almost unchanged even
after recycling the catalyst for five cycles.
Table 3 Chemical composition of polymer supported ligand (3) and Pd-PS-ala catalyst
(4)
Compound
Ligand (3)
C%
H%
N%
Pd%
74.96
6.36 4.61
-
Pd-PS-ala (4)
71.94
6.97 4.78
10.34 (10.23a)
aPalladium content of recycled catalyst after 5th cycles
3.2.1 IR study
Figure 2. DRS-UV-Visible spectra of ligand and Pd-PS-ala catalyst.
The mode of attachment of β-alanine and palladium metal onto the
support was confirmed by IR spectral bands (Figure 1). In the FT-IR
spectrum of aldehyde functionalized polymer (2), a new peak
appeared at 1705 cm-1 that was assigned to carbonyl C=O bond
stretching vibration of the aldehyde group. In the polymer (2) the
sharp C-Cl peak due to -CH2Cl group at 1264 cm-1 was absent.25 The
formation of the Schiff base moiety on the polymeric support (3) is
indicated by a peak at 1,633 cm-1 assigned to C=N stretching
frequency. This band shifted to lower wave numbers after
complexation with palladium metal. The polymer supported Pd-
catalyst (4) exhibited IR peaks at 1574 cm-1, 1423 cm-1 (ν COO
bridged).26 It suggests that, Schiff base coordinated to the central
palladium ion through the azomethine nitrogen.
3.2.3 Scanning electron micrographs (SEM) and energy dispersive
X-ray analysis (EDX)
The morphology of the catalyst was studied using Scanning Electron
Microscope (SEM). The micrographs of the polymer anchored β-
alanine ligand and palladium(II) catalyst obtained from the scanning
electron microscope are presented in Figures 3a and 3b
respectively. The morphological changes in the polymer supported
ligand and polymer supported catalyst are quite evident from these
images. The micrograph of five time reused Pd-PS-ala catalyst is
also presented in figure 3c. Quite uniform and negligible variation in
size is observed throughout the both specimens. Energy dispersive
spectroscopy analysis of X-rays (EDAX) data for the polymer
supported palladium complex is given in Figure 4. The EDAX data
also inform the attachment of palladium on the surface of the
polymer matrix.
Figure 1. FT-IR spectra of (2) aldehyde functionalised polymer, (3) polymer supported
schiff base ligand and (4) polymer supported Pd(II) catalyst, Pd-PS-ala.
4 | J. Name., 2012, 00, 1-3
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100
80
60
40
20
100
200
300
400
500
600
0
Temperature ( C)
Figure 5. TGA plots for Pd-PS-ala catalyst.
3.3 General Procedure for Coupling of Phenol with Allyl acetate
A mixture of polymer supported Pd(II) catalyst (30 mg), cinnamyl
acetate (1 mmol), p-cresol (1 mmol), potassium carbonate (2 mmol)
and water (3mL) was placed in a 10 mL round bottom flask and was
stirred for 16 h at 110 oC. The reaction was monitored by TLC. After
completion of reaction, the catalyst was removed by simple
filtration through celite-545. Then ethyl acetate was added to the
reaction mixture and the organic layer was separated from water.
The desired product was isolated from the extracted organic part by
column chromatography over silica gel (ethyl acetate/hexane) to
provide pure 1-(cinnamyloxy)-4-methylbenzene as colourless oil;
yield: 209 mg (90%). The spectroscopic data (1H NMR and 13C NMR)
of this product are in good agreement with those of an authentic
sample.
Figure 3. SEM images of (a) Polymer supported schiff base ligand, (b) Polymer
supported Pd(II) catalyst, Pd-PS-ala, (c) Five times recycled polymer supported
Pd(II) catalyst, Pd-PS-ala.
3.4 Heterogeneity Test
To verify the heterogeneity of the catalyst, 1 mmol p-cresol, 1 mmol
cinnamyl acetate and 30 mg catalyst were allowed to stir in 3 mL
water at 110 oC. The reaction was stopped after 8 h, and the
conversion was found to be 56 % by GC-analysis. At this stage, the
catalyst was separated from the reaction medium and the reaction
was continued with the filtrate for next 8 h. After total 16 h the
extent of conversion was found to remain the same. Moreover, UV-
Visible spectra of the catalyst free reaction mixture did not show
any absorption peak responsible for palladium. This information
indicates that the reaction was followed by a heterogeneous
pathway. Further, the leaching of palladium from the catalyst was
checked by analyzing (EDX, IR) the used catalyst. Analysis of the
used catalyst did not show appreciable loss in palladium content as
compared to that of fresh catalyst. Beside, IR-spectrum of the
recycled catalyst was quite similar to that of the fresh sample
indicating the heterogeneous nature of the catalyst. The UV-Visible
spectroscopy was also used to determine the stability of the
catalyst. The metal content of the recycled catalyst was determined
with the help of AAS and it was found that palladium content of the
recycled catalyst remained almost unchanged. These observations
strongly suggest that the catalyst is truly heterogeneous in nature.
Figure 4. EDAX data of polymer supported Pd(II) catalyst, Pd-PS-ala.
3.2.4 TGA Analysis
Thermal stability of the complex was investigated using TGA at a
heating rate of 10 oC/min in air over a temperature range of 30-600
oC. TGA curve of the polymer supported Pd(II) catalyst is shown in
Figure 5. The Pd(II)-complex is stable up to 370-390 oC and above
that temperature it is decomposed. Thermogravimetric study
suggests that the polymer supported palladium complex degrade at
considerably higher temperature.
3.5 Recovery of Catalyst
At the end of the reaction, the reaction mixture was filtered. Then
the recovered catalyst was thoroughly washed with methanol, dried
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and then further washed with diethyl ether to remove any traces of 13C NMR (75 MHz, CDCl3): δ 65.2, 68.9, 115.1 (2C), 124.5, 126.7,
organic materials. The catalyst was then finally dried at 55 oC for 5 h 128.1 (2C), 128.7 (2C), 128.8 (2C), 133.2, 136.6, 158.4; anal. calcd.
under vacuum to activate. The catalyst can be recycled for five for C16H16O2: C 79.97, H 6.71; found: C 80.06, H 6.68%.
times without losing the activity (Figure 6).
2-(4-(cinnamyloxy)-phenyl)-acetonitrile (Table 3, 3k): White Solid;
IR (KBr): 3406, 2924, 2853, 2251, 1953, 1731, 1612, 1512, 1462,
1247, 1014 cm-1; 1H NMR (400 MHz, CDCl3): δ 3.62 (s, 2 H), 4.63 (d, J
= 5.6 Hz, 2 H), 6.31-6.35 (m, 1 H), 6.66 (d, J = 16 Hz, 1 H), 6.89 (d, J =
8.4 Hz, 2 H), 7.16-7.35 (m, 7 H); 13C NMR (75 MHz, CDCl3): δ 22.8,
68.7, 114.0, 115.4 (2C), 118.1, 122.0, 124.1, 126.6 (2C), 127.9, 128.6
(2C), 129.1 (2C), 133.3, 158.4; anal. calcd. for C17H15NO: C 81.90, H
6.06, N 5.62; found: C 81.88, H 6.11, N 5.66%.
7-(3-phenyl-allyloxy)-quinoline (Table 3, 3m): Dirty white solid; IR
(KBr): ν 3382, 3066, 2959, 2863, 2752, 2682, 1634, 1598, 1442,
1381, 1221, 1040 cm-1; 1H NMR (400 MHz, CDCl3): δ 4.69 (d, J = 6
Hz, 2 H), 6.36-6.41 (m, 1 H), 6.68 (d, J = 16 Hz, 1 H), 7.27-7.48 (m, 7
H), 7.68 (d, J = 5.6Hz, 1 H), 7.83 (d, , J = 8.8 Hz, 1 H), 8.28 (d, J =
5.6Hz, 1 H), 9.09 (s, 1H); 13C NMR (75 MHz, CDCl3): δ 64.7, 108.3,
120.6, 123.7, 124.2, 126.5, 126.9 (2C), 128.4, 128.6, 129.0, 129.1
(2C), 131.1, 133.4, 140.3, 150.8, 156.7; anal. calcd. for C18H15NO: C
82.73, H 5.79, N 5.36; found: C 81.78, H 5.66, N 5.41%.
Figure 6. Recyclability chart for Pd-PS-ala catalyst.
The known compounds were identified by comparison of their
spectra with those of authentic samples 3a27a, 3b23a, 3c27b, 3d27b
,
3f23a, 3i27c, 3l27d, 3o27e, 3p23a, 3q19f, 3u27f. The unknown compounds
were properly characterized by their spectroscopic data (IR, 1H
NMR, 13C NMR and HRMS) data and elemental analysis and these
data are provided below in order of their numbers in the respective
tables and schemes.
(E)-1-bromo-4-((3-(p-tolyl)-allyl)-oxy)-benzene (Table 3, 3n): White
solid; IR (KBr): 3375, 2933, 2863, 1742, 1650, 1606, 1509, 1463,
1
1380, 1287, 1241, 1175, 1105, 1063, 1032 cm-1; H NMR (400 MHz,
CDCl3): δ 1.97 (s, 3 H), 4.58 (d, J = 6.0 Hz, 2 H), 6.26 (m, 1 H), 6.61 (d,
J = 16.0 Hz, 1 H), 6.76 (d, J = 8.8 Hz, 2 H), 7.06 (d, J = 8.0 Hz, 2 H),
7.23 (d, J = 8.0 Hz, 2 H), 7.29-7.32 (m, 2 H).; 13C NMR (75 MHz,
CDCl3): δ 21.8, 68.9, 114.0, 116.6 (2C), 122.8, 126.5, 126.6 (2C),
129.3 (2C), 132.2 (2C), 133.5, 137.9, 157.7; anal. calcd. for
C16H15BrO: C 63.38, H 4.99; found: C 63.41, H 4.83%.
1-[3-(3-phenyl-allyloxy)-phenyl]-ethanone (Table 3, 3e): Yellow
viscous oil; IR (neat): 3415, 3027, 2923, 2853, 1684, 1580, 1484,
1438, 1356, 1269, 1212, 1018 cm-1; 1H NMR (400 MHz, CDCl3): δ
2.46 (s, 3 H), 4.59 (d, J = 5.6 Hz, 2 H), 6.24-6.31 (m, 1 H), 6.62 (d, J =
15.6 Hz, 1 H), 7.02-7.29 (m, 7 H), 7.42 (d, J = 7.6 Hz, 2 H); 13C NMR
(75 MHz, CDCl3): δ 26.7, 68.9, 113.6, 120.3, 121.4, 124.0, 126.7 (2C),
128.1, 128.7 (2C), 129.7, 133.4, 136.4, 138.6, 158.9, 197.9; HR-MS
(EI): m/z=275.1046 (M+Na+), calcd. for C17H16O2: 275.1048.
1-(4-bromocinnamyloxy)-4-bromobenzene (Table 3, 3r): White
Solid; IR (KBr): 3368, 3081, 2932, 2854, 1780, 1604, 1591, 1496,
1463, 1378, 1290, 1175, 1117 cm-1; 1H NMR (400 MHz, CDCl3): δ
4.65 (d, J = 4.4 Hz, 2 H), 6.36-6.39 (m, 1 H), 6.66 (d, J = 16 Hz, 1 H),
6.83 (dd, J1 = 2 Hz, J2 = 4.8 Hz, 2 H), 7.27 (d, J = 7.6 Hz, 2 H), 7.38 (d, J
= 4.8 Hz, 2 H), 7.45 (d, J = 6.8 Hz, 2 H); 13C NMR (75 MHz, CDCl3): δ
67.6, 113.0, 115.5, 120.8, 123.7, 127.7, 127.1, 130.7, 130.9, 131.3,
138.3, 156.7; anal. calcd. for C15H12Br2O: C 48.95, H 3.29; found: C
48.88, H 3.34%.
1,3-Dimethoxy-2-(3-phenyl-allyloxy)-benzene (Table 3, 3g): Pale
Yellow Solid; IR (KBr): 3417, 3036, 2989, 2958, 2865, 1889, 1609,
1510, 1460, 1252, 1241, 1177, 1112, 1031 cm-1; H NMR (400 MHz,
1
CDCl3): δ 3.78 (s, 6 H), 4.59 (d, J = 6.0 Hz, 2 H), 6.45-6.53 (m, 1 H),
6.65 (dd, J1 = 7.6 Hz, J2 = 16 Hz, 3 H), 6.91 (d, J = 8.4 Hz, 1 H), 7.41 (d,
J = 15.6 Hz, 2 H), 7.45-7.51 (m, 3 H); 13C NMR (75 MHz, CDCl3): δ
56.1 (2C), 73.8, 105.4 (2C), 123.7, 123.9, 126.5 (2C), 128.2, 128.65
(2C), 129.1, 132.9, 152.6 (2C), 153.8; anal. calcd. for C17H18O3: C
75.53, H 6.71; found: C 74.98, H 6.65%.
1-(2-methoxycinnamyloxy)-4-methyl benzene (Table 3, 3s): Pale
yellow solid; IR (KBr): 3397, 3031, 2958, 2914, 2840, 2052, 1895,
1655, 1606, 1510, 1461, 1383, 1328, 1283, 1241, 1177, 1111, 1031
cm-1; 1H NMR (400 MHz, CDCl3): δ 2.21 (s, 3 H), 3.77 (s, 3 H), 4.59 (d,
J = 0.8 Hz, 2 H), 6.33-6.4 (m, 1 H), 6.78-6.87 (m, 4 H), 6.95-7.02 (m, 3
H), 7.14-7.18 (m, 1 H), 7.39 (dd, J1 = 1.2 Hz, J2 = 7.6 Hz, 1 H); 13C
NMR (75 MHz, CDCl3): δ 22.3, 55.0, 68.9, 110.5, 114.3 (2C), 120.2,
125.0, 125.2, 126.8, 127.7, 128.5, 129.6 (2C), 129.5, 156.3, 156.4;
anal. calcd. for C17H18O2: C 80.28, H 7.13; found: C 80.67, H 7.11%.
1-Fluoro-4-(3-phenyl-allyloxy)-benzene (Table 3, 3h): White Solid;
IR (KBr): 3564, 3390, 3020, 2854, 1635, 1506, 1215 cm-1; 1H NMR
(400 MHz, CDCl3): δ 4.59 (d, J = 1.2 Hz, 2 H), 6.31-6.36 (m, 1 H), 6.65
(d, J = 16 Hz, 1 H), 6.81-6.84 (m, 2 H), 6.89-6.93 (m, 2 H), 7.18-7.21
(m, 2 H), 7.24-7.27 (m, 2 H), 7.33-7.35 (m, 2 H); 13C NMR (75 MHz,
CDCl3): δ 69.5, 114.2, 116.0 (d, J = 18.7 Hz, 2C), 116.1, 124.5 (2C),
126.7 (2C), 128.7 (2C), 133.3, 136.6, 155.8 (d, J = 207.5 Hz, 1C),
158.7; anal. calcd. for C15H13FO: C 78.93, H 5.74; found: C 78.81, H
5.82%.
(2E)-3-(4-(cinnamyloxy)-phenyl)-1-phenylprop-2-en-1-one (Table
3, 3t): White Solid; IR (KBr): 3393, 3026, 2923, 2853, 1904, 1660,
1631, 1601, 1509, 1445, 1381, 1333, 1290, 1248, 1178, 1113, 1070,
1
1008 cm-1; H NMR (400 MHz, CDCl3): δ 4.76 (dd, J1 = 1.2 Hz, J2 = 6
(4-(cinnamyloxy)phenyl)methanol (Table 3, 3j): Yellowish viscous
liquid; IR (neat): 3645, 3583, 3415, 3361, 3294, 3242, 2927, 2856,
1747, 1650, 1508 cm-1; 1H NMR (400 MHz, CDCl3): δ 4.65 (s, 2H),
4.73 (d, J = 6.5 Hz, 2H), 6.41-6.47 (m, 1H), 6.76 (d, J = 16.0 Hz, 1H),
6.98 (d, J = 8.4 Hz, 1H), 7.26-7.34 (m, 5H), 7.36 (d, J = 7.6 Hz, 2H);
Hz, 2 H), 6.38-6.45 (m, 1 H), 6.75 (d, J = 16 Hz, 1 H), 6.99 (d, J = 8.8
Hz, 2 H), 7.26-7.28 (m, 1 H), 7.32-7.36 (m, 2 H), 7.41-7.44 (m, 3 H),
7.48-7.52 (m, 2 H), 7.56-7.58 (m, 1 H), 7.59-7.63 (m, 2 H), 7.79 (d, J
= 15.6 Hz, 1 H), 8.00-8.02 (m, 2 H); 13C NMR (75 MHz, CDCl3): δ 68.7,
6 | J. Name., 2012, 00, 1-3
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ARTICLE
and K. B. Sharpless, J. Org. Chem., 2001, 66, 7945; (c) C. J.
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115.2 (2C), 119.9, 123.7, 126.6 (2C), 127.8, 128.0, 128.3 (2C), 128.4
(2C), 128.5 (2C), 130.2 (2C), 132.5, 133.4, 136.2, 138.5, 144.6, 160.7,
190.5; HR-MS (EI): m/z=341.1542 (M+H+), calcd. for C24H20O2:
341.1540.
4
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,
1-Chloro-4-(3-phenyl-allyloxymethyl)-benzene (Scheme 4, 5a):
Yellow viscous liquid; IR (neat): 3355, 3050, 2952, 2920, 2760, 1911,
1605, 1490, 1468, 1360, 1298, 1288, 1274, 1109, 1085 cm-1; 1H
NMR (400 MHz, CDCl3): δ 4.26 (d, J = 4.4 Hz, 2 H), 4.59 (s, 2 H), 6.27-
6.34 (m, 1H), 6.56 (d, J = 16.0 Hz, 1 H), 7.21-7.36 (m, 9 H); 13C NMR
(75 MHz, CDCl3): δ 63.0, 63.7, 126.0 (2C), 127.3, 127.8 (2C), 127.9,
128.1 (4C), 130.7, 132.8, 136.3, 138.9; anal. calcd. for C16H15ClO: C
74.27, H 5.84; found: C 74.21, H 5.66%.
5
6
S. M. Islam, A. S. Roy, P. Mondal and N. Salam, Applied
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7
8
S. M. Islam, A. S. Roy, P. Mondal and N. Salam, Journal of
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Conclusions
In conclusion, we have demonstrated the synthesis of polymer
supported air- and moisture-stable, oxygen-insensitive and
reusable palladium(II) catalyst and its application for the O-
allylation of allyl/cinnamyl acetates with substituted phenol
under refluxing condition in water. Ease of recovery and reuse
of the catalyst make this method an economic and
environmentally-benign process. In addition, high yields,
excellent stereo- specificity, use of water as solvent, scope of
wide functionalization and simple work-up procedure make
this method more attractive and valuable to the existing
methodologies for allylic C-O coupling reactions.
9
10 (a) A. Monte, M. S. Kabir, J. M. Cook, M. Rott, W. R. Schwan
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Acknowledgements
SA thanks Prof. Abu T. Khan of the Aliah University, Kolkata for
his support. SMI gratefully acknowledges Department of
Science and Technology (DST), New Delhi, India for funding
(Project No. SB/S1/PC-107/2012 Dated: 10.06.2013). We
acknowledge DST and UGC for providing support to the
University of Kalyani under FIST, Purse and SAP programme.
M.H. acknowledges Dr. Kamalika Sen and Dr Anupam Singha
Roy for his entire help and expresses sincere thanks to the
UGC for providing necessary fellowship. MMI acknowledges
UGC, New Delhi for Maulana Azad National Fellowship.
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