J. Serb. Chem. Soc.

76 (2) 155163 (2011)

JSCS4108

UDC 66.095.11+547.857.8:678.746:547316
Original scientific paper

FriedelCrafts acylation of arenes with carboxylic acids

using polystyrene-supported aluminum triflate
KAVEH PARVANAK BOROUJENI1* and KAMRAN PARVANAK2
1Department

of Chemistry, Shahrekord University, Shahrekord 115 and

Azad University, Shahr-e-Rey Branch, Iran

2Islamic

(Received 15 February, revised 1 September 2010)

Abstract: Cross-linked polystyrene-supported aluminum triflate (PsAl(OTf)3)
has been shown to be a mild, efficient, and chemoselective heterogeneous
Lewis acid catalyst for the acylation of aromatic compounds. The catalyst can
be easily prepared from cheap starting materials, is stable (as a bench top catalyst) and is reusable.
Keywords: acylation; ketones; aluminum triflate; polystyrene.
INTRODUCTION

FriedelCrafts acylation of arenes is of great importance in both laboratory

work and industry processes to synthesize aromatic ketones.1,2 Usually, this reaction is performed using acid chlorides or anhydrides312 or carboxylic acids1325
as acylating agents in the presence of protic acids or Lewis acids. Acylation of
arenes using carboxylic acids is preferable to the acylation via acid chlorides or
anhydrides because the former reaction produces only water as a by-product,
which meets recent requirements for environmentally benign chemical processes.
Furthermore, carboxylic acids are stable and more available compounds and their
handling is much easier than that of the corresponding acid chlorides or anhydrides. However, only a few studies on the use of carboxylic acids as acylating
agents have been reported and many of these procedures have serious drawbacks,
such as a need for the use of stoichiometric or excess amounts of catalyst in the
reactions, tedious work-up, environmental pollution, long reaction times, high
reaction temperatures, highly corrosive conditions, the formation of various byproducts and the use of moisture-sensitive, non-recyclable or difficult to handle
catalysts. In view of this, a reliable method for this useful reaction involving
heterogeneous catalysts is demanded.
* Corresponding author. E-mail: parvanak-ka@sci.sku.ac.ir
doi: 10.2298/JSC100215010P

155

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BOROUJENI and PARVANAK

Triflic acid (trifluoromethanesulfonic acid), known to be a strong acid, is

suitable for use as a catalyst for synthetic applications.2628 However, the recovery of the triflic acid from the reaction mixture results in the formation of
large amounts of waste, which is environmentally unacceptable. In continuation
of our ongoing program to develop environmentally benign methods using heterogeneous Lewis acid catalysts, it was found that PsAl(OTf)3 is a good solid
catalyst for highly chemoselective dithioacetalization of carbonyl compounds.29
Along this line, it is herein reported that PsAl(OTf)3 is also an effective and
highly chemoselective catalyst for the acylation of aromatic compounds with
carboxylic acids under mild reaction conditions (Scheme 1).

Scheme 1. Acylation of arenes with carboxylic acids using PsAl(OTf)3.

EXPERIMENTAL
The employed chemicals were either self-prepared or were purchased from Merck and
Fluka. Polystyrene (8 % divinylbenzene, prepared via suspension polymerization, using poly(vinylpyrrolidone) 90 K as the suspension agent, grain size range: 0.250.6 mm) was obtained
from the Iran Polymer and Petrochemical Institute. Capacity of the catalyst was determined by
gravimetric method and atomic absorption technique using a Philips PU9400X atomic absorption spectrophotometer. Reaction monitoring and purity determination of the products were
accomplished by GLC or TLC on silica-gel polygram SILG/UV254 plates. Gas chromatography was performed on a Shimadzu GC 14-A. The IR spectra were recorded on a Shimadzu
model 8300 FT-IR spectrophotometer. The NMR spectra were recorded on a Bruker Advance
DPX-300 spectrometer.
Preparation of PsAl(OTf)3
This catalyst was prepared as reported in the literature.29 The determined loading of
Al(OTf)3 was 0.41 mmol g-1.
Typical experimental procedure
To a solution of arene (5 mmol) and carboxylic acid (3.5 mmol) was added 0.35 mmol of
PsAl(OTf)3 and the reaction mixture was stirred at 80 C. After completion of the reaction
(monitored by TLC and GC), the catalyst was filtered off and washed with CH2Cl2. The filtrate was washed with 10 % NaHCO3 solution (210 mL) and water (210 mL) and the organic layer was dried over anhydrous Na2SO4. The unreacted anisole was removed by vacuum
distillation and the aryl ketone product was isolated in high purity in yields from 87 to 97 %.
Whenever required, the products were purified by column chromatography (silica gel) using
petroleum etherethyl acetate as the eluent, whereby pure ketone was obtained.
RESULTS AND DISCUSSION

PsAl(OTf)3 was prepared by the exchange reaction between cross-linked

polystyrene supported AlCl3 (PsAlCl3) and triflic acid in Freon-113 under reflux conditions. Using catalytic amounts of this catalyst in the FriedelCrafts

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FRIEDELCRAFTS ACYLATION

acylation of arenes with carboxylic acids as acylating agents under solvent-free

conditions, high to excellent yields of product were obtained (Table I). The
optimum molar ratio of PsAl(OTf)3 to carboxylic acid was 0.1:1. From the
results, it is clear that PsAl(OTf)3 is capable of catalyzing not only the acylation
of activated arenes, but also of deactivated arenes (Table I, entries 123). The
methodology showed the excellent positional selectivity as the para substituted
product was formed almost exclusively. Naphthalene, 2-methoxynaphthalene and
anthracene underwent acylation with high regioselectivity in 8793 % yields
(Table I, entries 2430). It was satisfying to observe that even heterocyclic
compounds, such as furan, thiophene and pyrrole, were smoothly converted into
the corresponding ketones, a conversion which is otherwise problematic in the
presence of strong acid catalysts (Table I, entries 3136). These reactions were
regioselective, affording only the 2-acyl product in high to excellent yields. The
acylation of indole with benzoic acid in the presence of PsAl(OTf)3 was also
studied and the corresponding indolyl aryl ketone was obtained with high
regioselectivity in 90 % yield (Table I, entry 37). No N-substituted products were
observed under these reaction conditions. Acylation of highly deactivated arenes,
such as nitrobenzene and 1,2-dichlorobenzene failed.
TABLE I. Acylation of arenes with carboxylic acids catalyzed by PsAl(OTf)3 (all reactions
performed at 80 C in the absence of solvent, unless otherwise indicated. The molar ratio of
PsAl(OTf)3:carboxylic acid is 0.1:1)
Entry

Arene

Carboxylic acid

PhCO2H

PhCO2H

p-NO2C6H4CO2H

CH3(CH2)2CO2H

CH3(CH2)5CO2H

CH3(CH2)6CO2H

CH3(CH2)10CO2H

PhCO2H

p-MeOC6H4CO2H

10

MeCO2H

Product

Time Yield, %
Ref.
h
(o:m:p)a
3.3
90
20,30

3
92
25
(6:3:91)
3.1
90
25
(3:0:97)
2.9
95
13
(4:3:93)
2.9
94
13
(5:3:92)
3
88
13
(4:0:96)
3.1
85
13
(4:0:96)
3
94
25
(4:0:96)
2.9
95
15,25
(5:3:92)
2.9
94
3133
(6:4:90)

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TABLE I. Continued
Entry

Arene

Carboxylic acid

Product

Time Yield, %
h
(o:m:p)a
2.8
94
(6:4:90)
3.1
90
(3:0:97)
2.7
97
(5:4:91)
2.8
95
(5:3:92)
3
93
(3:0:97)
3
92
(3:0:97)
3
90
(95:5)b

Ref.

11

PhCH2CO2H

12

PhCH=CHCO2H

13

CH3(CH2)2CO2H

14

CH3(CH2)5CO2H

15

CH3(CH2)6CO2H

16

CH3(CH2)10CO2H

17

CH3(CH2)5CO2H

18

PhCO2H

2.9

93

25

19

MeCO2H

2.8

94

18,36

20

PhCO2H

3.1

30

21

PhCO2H

22

PhCO2H

3.5

23

MeCO2H

3.3

24

MeCO2H

3.3

88
(3:4:97)c
91
(7:3:90)
87
(4:3:93)
89
(5:3:92)
88
(3:97)c,d

25

PhCO2H

3.1

93c

34
25,35
16,18
16,18
16,18
16,18
21

7,30
30
30
18
25

26

p-NO2C6H4CO2H

90c

25

27

MeCO2H

3.1

90c

18,37

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FRIEDELCRAFTS ACYLATION

TABLE I. Continued
Entry
28

Arene

Carboxylic acid

Product

PhCH2CO2H

Time Yield, %
Ref.
h
(o:m:p)a
3
90c
18,38

29

PhCO2H

3.4

87c

25

30

MeCO2H

3.3

89c

18,37

31

PhCO2H

3.5

89e

20,39

32

MeCO2H

3.3

90e

5,40

33

p-NO2C6H4CO2H

3.6

89e

34

MeCO2H

3.6

92e

5,41

35

PhCO2H

3.4

87e

5,42

36

MeCO2H

3.3

89e

18,42

37

PhCO2H

90c

4345

aIsolated yields. Isomer distribution based on 1H-NMR spectroscopy and GC. All products are known com-

pounds and were identified by comparison of their physical and spectral data with those of authentic samples;
bisomer distribution of the 3,4-dimethylphenyl isomer to the 2,3-dimethylphenyl isomer; cthe reaction was
performed in 1,2-dichloroethane; d: ratio; ethe reaction was performed at 60 C.

When PsAl(OTf)3 was used as the catalyst in the acylation reactions, no

band corresponding to CO stretching in the IR spectrum of PsAl(OTf)3 was
observed after the reactions in either the presence or absence of substrate, indicating that polystyrene itself did not undergo acylation under the employed
experimental conditions. Probably acylation reactions are not favored with Ps
Al(OTf)3 as a complex is formed between the polystyrene and Al(OTf)3.29,46
By-product formation was not observed in the studied reactions. Steric crowding

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BOROUJENI and PARVANAK

of the supported catalyst influences the positional selectivity (isomer distribution)

observed in the acylation of aromatic compounds.
To determine whether the reaction occurs in the solid matrix of PsAl(OTf)3
or whether Al(OTf)3 simply released into the reaction medium is responsible for
the acylation reaction, PsAl(OTf)3 was added to toluene and the mixture was
stirred at 80 C for 2 h. Then, the catalyst was filtered off and the filtrate was
analyzed for its aluminum content, which showed a negligible release of Al(OTf)3.
The filtrate was found to be inactive for acylation reaction. These observations
indicate that PsAl(OTf)3 is stable under the employed reaction conditions and
there was no leaching of acid moieties during the studied reactions.
One notable achievement of this solid acid catalyst was intramolecular FriedelCrafts acylation. For example, 4-phenylbutanoic acid cyclized in nitrobenzene at 80 C in the presence of PsAl(OTf)3 to afford the desired 1-tetralone in
94 % yield (Scheme 2).

Scheme 2. Intramolecular FriedelCrafts acylation using PsAl(OTf)3.

PsAl(OTf)3 recovered after a reaction can be washed with dichloromethane

and used again at least five times without any noticeable loss of catalytic activity
(Scheme 3). The capacity of the catalyst after five uses was 0.40 mmol Al(OTf)3
per gram of polymeric catalyst.

Scheme 3. Acylation of toluene using recovered PsAl(OTf)3 (recovered catalyst was

successfully reused).

A comparison of the efficiency of PsAl(OTf)3 catalyst with some of those

reported in the literature is given in Table II. As can be seen, in addition to having the general advantages attributed to solid supported catalysts, PsAl(OTf)3
also has good efficiency compared to other recently reported catalysts.
Representative spectral data of some of the obtained compounds are given
below.

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FRIEDELCRAFTS ACYLATION

161

TABLE II. Comparison of the catalytic activity of PsAl(OTf)3 against other reported catalysts for the acylation of anisole and toluene with carboxylic acids
Arene Carboxylic acid
Anisole
Benzoic acid

Anisole

Heptanoic acid

Anisole

Octanoic acid

Anisole Dodecanoic acid

Toluene

Octanoic acid

Catalyst
PsAl(OTf)3
AlPW12O40
AlPW12O40/TFAAa
P2O5/Al2O3
PsAl(OTf)3
HZSM-5 zeolite
Eu(NTf2)3
PsAl(OTf)3
Cs2.5H0.5PW12O40
Beta zeolite
PsAl(OTf)3
FePW12O40
PsAl(OTf)3
CeNaY zeolite

Temperature, C Time, h Yield, % (o:p)

80
3
94(4:96)
120
10
9218
25
2.5
9618
85
5
6525
80
2.8
95(5:92)
150
48
514
250
6
87(3:97)21
80
3
93(3:97)
110
5
45(1:73)16
155
6
42.6(1:38)22
80
3
92(3:97)
160
1
97(2:98)24
80
3
88(4:96)
150
48
75(3:94)13

Trifluoroacetic anhydride

4-Methylbenzophenone. IR (KBr, cm1): 1660 (C=O). 1H-NMR (300 MHz,

CDCl3, / ppm): 2.51 (3H, s), 7.51 (2H, d, J = 8.31 Hz), 7.878.15 (7H, m).
1-(4-Methoxyphenyl)-3-phenyl-2-propen-1-one. IR (KBr, cm1): 1650 (C=O).
1H-NMR (300 MHz, CDCl , / ppm): 3.91 (3H, s), 6.99 (2H, d, J = 8.71 Hz),
3
7.47 (3H, m), 7.59 (1H, d, J = 15.15 Hz), 7.69 (2H, m), 7.86 (1H, d, J = 15.15
Hz), 8.11 (2H, d, J = 8.71 Hz).
1-(3,4-Dimethylphenyl)-1-heptanone. IR (KBr, cm1): 1685 (C=O). 1H-NMR
(300 MHz, CDCl3, / ppm): 0.820.91 (3H, m), 1.231.41 (6H, m), 1.631.74
(2H, m), 2.262.33 (6H, m), 2.80 (0.1H, t, J = 7.2Hz, 2,3-dimethyl isomer), 2.90
(1.9H, t, J = 7.2 Hz, 3,4-dimethyl isomer), 7.11 (0.05H, t, J = 7.2 Hz, 2,3-dimethyl isomer), 7.137.20 (1H, m), 7.25 (0.05H, d, J = 7.2 Hz, 2,3-dimethyl
isomer), 7.65 (0.95H, d, J = 7.2 Hz, 3,4-dimethyl isomer), 7.70 (0.95H, d, J = 7.2
Hz, 3,4-dimethyl isomer).
2,4,6-Trimethylbenzophenone. IR (KBr, cm1): 1669 (C=O). 1H-NMR (300
MHz, CDCl3, / ppm): 2.2 (6H, s, 2- and 6-Me), 2.4 (3H, s, 4-Me), 6.91 (2H, s,
aromatic protons of mesityl group), 7.45 (2H, m), 7.55 (1H, m), 7.81 (2H, m).
1-Benzoyl-2-methoxynaphthalene. IR (KBr, cm1): 1665 (C=O). 1H-NMR
(300 MHz, CDCl3, / ppm): 3.88 (3H, s), 7.317.52 (7H, m), 7.558.12 (4H, m).
CONCLUSIONS

In conclusion, a convenient and chemoselective method of the acylation of

aromatic compounds has been devised. The significant advantages of this methodology are mild reaction conditions, high to excellent yields, solvent-free
conditions and easy preparation and handling of the catalyst. In addition, the use

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BOROUJENI and PARVANAK

of PsAl(OTf)3 resulted in a reduction in the unwanted and hazardous waste that

is produced during conventional homogeneous processes.
Acknowledgements. We gratefully acknowledge the partial support of this study by the
Shahrekord University and the Islamic Azad University, Shahr-e-Ray branch Research Council, Iran.

-
KAVEH PARVANAK BOROUJENI1 KAMRAN PARVANAK2
1

Department of Chemistry, Shahrekord University, Shahrekord 115 2Islamic Azad University,

Shahr-e-Rey Branch, Iran

- , o .
, je
.
( 15. , 1. 2010)

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