98

Catalysis Surveys from Asia, Vol. 10, No. 2, June 2006 ( 2006)
DOI: 10.1007/s10563-006-9007-8

Advances in liquid-phase Friedel-Crafts acylation of aromatics

catalyzed by heterogeneous solidsq
Suman K. Jana*
Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-Ku, Yokohama 226-0583, Japan

In the last few decades, signicant improvements toward the development of environmentally benign processes have been
achieved in the liquid-phase Friedel-Crafts acylation reactions. Many efforts have been devoted to the research on solid catalysts
adequate to substitute homogeneous protonic acids or Lewis acids as traditionally employed catalysts in the acid-catalyzed FriedelCrafts acylation processes. This short article describes the recent developments on catalysis by gallium (Ga), indium (In) and
thallium (Tl) based novel heterogeneous solids for the liquid-phase Friedel-Crafts acylation of aromatics by acyl halide. The above
heterogeneous catalysts are efcient for Friedel-Crafts acylation reaction and exhibited superior activity than the traditionally
employed strongly acidic solid catalysts. Unlike conventional acidic catalyst, the acylation activity of Ga, In and Tl based solids,
additionally having redox functions, does not depend solely on their acidic properties, even present. These solids in their non-acidic
or basic form also show high acylation activity. Based on the catalytic results over these novel solids a plausible reaction mechanism
for the acylation is proposed.
KEY WORDS: Friedel-Crafts acylation; heterogeneous catalysis; aromatics; acyl halide; zeolite; metal oxide; clay; gallium;
indium; thallium.

1. Introduction
Aromatic ketones are important chemical intermediates in the pharmaceutical, fragrance, avor, dye and
agrochemical industries [1,2]. Conventionally, these are
produced by electrophilic acylation of aromatic compounds with various acylating agents (e.g. acyl halide,
acid anhydride and acid) catalyzed by homogeneous
Lewis acids (e.g. AlCl3, BF3, FeCl3, ZnCl2, SnCl4, TiCl4,
etc.) or strong protonic acids (e.g. H2SO4, HF, etc.) as
follows [3]:
CO -R

H
(Z)p

R- CO-X

C atalyst

(Z)p

HX

[(Z)pArH = aromatic compound; (Z)p = substituent

group(s);
RCOX = acylating
agent;
R = alkyl or phenyl group; X = Cl, Br, I; RCOO or
OH]
However, the major limitation particularly the use of
metal halide catalyst in the acylation is associated with
the formation of strong complex between the product
ketone and the metal halide itself. Because of the above
reason the use of even more than stoichiometric amount
q
Dedicated to Professor Seitaro Namba on the occasion of his 64th
birthday.
*To whom correspondence should be addressed.
E-mail: suman@cat.res.titech.ac.jp

of catalyst is employed in the liquid-phase acylation

reactions. Additionally, the workup requires hydrolysis
of the complex, which leads to the formation of large
amounts of corrosive waste and the loss of catalyst [3,4].
Hence the development of more eco-friendly processes
for the Friedel-Crafts acylations has become a fundamental goal as a perspective of green chemistry for the
researchers working in this area.
Eorts have been made by dierent research groups
to achieve this goal by developing new acidic catalyst for
Friedel-Crafts acylation reactions. Interesting results
have been achieved by the use of catalytic amounts of
lanthanide triuoromethanesulfonate based catalysts
[5,6]. Although, the above result indicates some practical
developments but they have not led to any important
industrial applications.
Heterogeneous acidic catalysts in the liquid-phase
have certain advantages over the homogeneous ones.
They oer easier separation and recovery of the products and catalyst from the reaction mixture. They are
reusable, generally not corrosive and do not generate
problematic side product(s). Additionally they contribute shape selectivity to the product. Thus shape selective
heterogeneous catalysts are very capable of replacing
traditional homogeneous Friedel-Crafts catalysts.
Because of the above advantages, major research eorts
have been directed toward the development of shape
selective solid catalyst for the synthesis of acylated
aromatics over the past decade. A number of heterogeneous catalysts based on zeolites [714], metal oxides
1571-1013/06/06000098/0 2006 Springer Science+Business Media, Inc.

S.K. Jana/Friedel-Crafts acylation of aromatics

[1524], clays [2529], heteropoly acids [28,3032] and

sulfonic acids [33] have been reported by dierent
research groups so far for Friedel-Crafts acylation
reactions.
The present article describes some advances in the
liquid-phase Friedel-Crafts acylation reaction (by acyl
chloride) catalyzed by gallium, indium and thallium
containing heterogeneous novel solids ranging from
acidic to basic types recently developed by the author.
For the rst time, author reported that not only acidic
catalysts but also non-acidic or even basic solid could
catalyze Friedel-Crafts acylation of benzene and other
aromatic compounds. These novel solid catalysts,
additionally having redox functions, are very active/
selective in the acylation process and their activities are
found to be higher than the strongly acidic heterogeneous catalysts reported in the literature.

2. Friedel-Crafts acylation catalyzed by various

heterogeneous solids
2.1 Catalysis by zeolites
Zeolites are microcrystalline porous solids and largely
applied as catalysts in petrochemical industry [34].
Nowadays the interest for the use of zeolites in manufacturing ne and specialty chemicals as well as pharmaceuticals is increasing rapidly [35].
Among the various types of zeolites, beta, Y, mordenite, MCM-22 and ZSM-5 are widely used catalysts for
Friedel-Crafts acylation reactions [714]. It is reported
that, the activity of zeolite in the liquid-phase acylations
largely depends on their structural features and the
activity increases from medium to large pore and from
mono to three dimensional channel systems [7]. Because
of the above reasons, beta zeolite having distorted
channel structure with three mutually intersecting 12ring channels is found to be the best and most suitable
zeolite catalyst for Friedel-Crafts acylation of aromatics
as compared to the others. The pore types and dimensions of the above ve zeolites are depicted in table 1. It
is important here to note that, although beta zeolite
showed high activity in the acylation of activated aro-

Table 1
Pore type and dimensions of various microporous zeolites commonly
used in the Friedel-Crafts acylation reactions
Zeolite
Beta
ZSM-5
Mordenite
Y
MCM-22
a

Pore type
Interconnected
Interconnected
Interconnected
Interconnected
Interconnected

channels
channels
channels
spheres
channels

Dimensionsa (nm)
0.66
0.67, 0.56
0.56
0.55
0.51, 0.56
0.53
0.70
0.65
0.74
0.55
0.40, 0.51
0.41

Ch. Baerlocher et al., "Atlas of zeolite framework types", 5th ed.

Elsevier (2001).

99

matics by acyl halide but its activity for non-activated

aromatics (e.g. benzene) is not so impressive.
During my doctoral research at NCL (National
Chemical Laboratory, Pune, India) with Dr. Choudhary, we found that the catalytic activity of Hb
zeolite is dramatically increased after its modication
by Ga2O3 or In2O3 for the acylation process even
under solvent-free conditions [3638]. Catalytic results
along with some catalyst characterization data are
presented in table 2. Hb zeolite without modication
showed very low activity in the benzene benzoylation
reaction (30% conversion of benzoyl chloride in 12 h).
However, the activity (expressed in terms of the time
required for half the reaction, t1/2, based on 50%
conversion of acylating agent) is increased drastically
after its modication by impregnation of the zeolite
with Ga or In (table 2). The increase in activity of the
modied catalysts seems to be not responded for its
acidity. Because, the strong acid sites (measured in
terms of ammonia chemisorbed at 250 C) of the
zeolite catalysts are decreased signicantly after modication. This is expected because of the replacement
of some acidic zeolitic protons by the metal cations.
Similar phenomenon was reported earlier for the
Ga2O3 impregnated H-ZSM-5 zeolite catalyst for the
lower alkane aromatization [39]. Interestingly, it is
observed that among the Ga2O3 and In2O3 modied
zeolites, In2O3 supported on Hb showed higher
activity as compared to the Ga2O3 ones for the benzene benzoylation reaction, although the acidity of
Ga2O3/Hb is slightly higher than that of In2O3/Hb.
The In2O3/Hb is also exhibited high activity for benzoylation of a variety aromatic compound by benzoyl
chloride at 80 C (table 3). It is found that the conversion of benzoyl chloride in the benzoylation of
substituted aromatics over In2O3/Hb catalyst depends
strongly upon the substituent group(s) present in the
aromatic substrate. The activity of the catalyst is increased due to the presence of electron-donating
group(s), depending upon its electron-donating ability.
The order of the catalytic activity for the benzoylation
of dierent aromatic compounds is as follows: benzene
< < methyl benzene (toluene) < di-methyl benzene
(p-xylene) < methoxy benzene (anisole). Additionally,
it is observed that in the case of substituted benzenes
the formation of p-benzoylated product is favored
over the o-benzoylated one; the formation of m-benzoylated product is found to be very small.
Above results indicate that, zeolitic acidity plays an
important role for deciding the catalytic activity of beta
zeolite in the acylation process; however, the acidity
alone seems to be not enough for making Hb a highly
active catalyst for the acylation reaction by acyl halide.
The zeolitic acid sites along with the presence of Ga2O3
or In2O3 are responded for enhancing the reaction rate
in the benzoylation over Ga2O3 or In2O3 supported Hb
catalyst.

100

S.K. Jana/Friedel-Crafts acylation of aromatics

Table 2
Physico-chemical properties and benzene benzoylation activities [reaction conditions: reaction mixture = 145.5 mmol benzene + 8.6 mmol
benzoyl chloride + 0.4 g catalyst, reaction temperature = 80 C] of Hb zeolite with or without its modication by Ga or In
Catalyst

Hb
In2O3 (20%)/Hb
Ga2O3 (20%)/Hb
a

Surface area
(m2g)1)

685
562
607

Ammonia
chemisorbed
(mmolg)1)

Induction
perioda (min)

50 C

250 C

2.15
1.99
2.00

1.10
0.66
0.73

0.3
0.6

Time required for

half the reaction
(h)

30% conversion in 12 h
3.9
5.7

TON for half

the reaction
(h)1)

1.9
0.9

Time elapses between the start of reaction and the formation of a benzoylated product.

Table 3
Catalytic performance of In2O3 (20 wt%)/Hb in the acylation of various aromatics by benzoyl chloride [reaction conditions: reaction
mixture = 145.5 mmol aromatic compound + 8.6 mmol benzoyl chloride + 0.4 g catalyst, reaction temperature = 80 C]
Aromatic
compound
Benzene
Toluene
p-Xylene
Anisole
a

Induction perioda
(min)
5.4
3.2
2.9
2.3

Time required for half

the reaction (min)

Reaction product(s)
(Selectivity%)

234
47
30
17

Benzophenone ( > 99%)

p-Benzoylated (89%) and o-benzoylated (11%)
2,5-Di-methyl benzophenone ( > 99%)
p-Benzoylated (90%) and o-benzoylated (10%)

Time elapses between the start of reaction and the formation of a benzoylated product.

Recently, Hutchings et al. also reported that the

incorporation of redox metal, Fe, drastically increased
the catalytic activity of NaY in the benzoylation of
toluene by benzoyl chloride [14]. They found that the
catalytic activity of FeNaY zeolite is even higher when
compared with homogeneous FeCl3 catalyst under
identical liquid-phase reaction conditions.
It is important here to note that the catalytic activity
of microporous beta and Y zeolites showing high
activity in the acylation of aromatics are restricted only
for the aromatic substrate having kinetic diameter up to
8 A. This is because of the limited dimensions and pores
of zeolite cage in which reactant molecules with kinetic
diameter higher than 8 A cannot be accessible to the
internal active sites of the zeolite. It is, therefore, very
important to explore the use mesoporous molecular
sieve with a diameter greater than 20 A particularly for
the synthesis of industrially important large aromatic
ketones.
Mesoporous MCM-41 possessing a hexagonal
arrangement of uni-dimensional pores with diameter
ranging from 20 to 100 A is recently attracted more
attention for its catalytic use in the liquid-phase transformation of bulky organic compounds [40]. However,
the report on the use of mesoporous material for Friedel-Crafts acylation reaction is scarce. Recently, we
modied mesoporous Si-MCM-41 by both the oxides
and chlorides of Ga and In [4146]. In this section, I will
discuss the results on modication of Si-MCM-41 by
chlorides of Ga and In, the modication by oxides will
be described later. The benzene benzoylation activity
(measured in terms of t1/2) of Si-MCM-41 with or

without its modication by GaCl3 or InCl3 is compared

in table 4. Data in table 4 indicates that, high silica
mesoporous MCM-41 shows almost no catalytic activity
in the benzoylation reaction. Even acidic H.Al-MCM-41
is also found to be quite inactive for the above reaction.
However, the catalytic activity of Si-MCM-41 is
abruptly increased after its modication by the
impregnation of GaCl3 or InCl3 from their non-aqueous
solution. Among the supported GaCl3 and InCl3 catalysts, the supported InCl3 showed higher activity in the
benzene benzoylation reaction under solvent-less conditions, although the Lewis acidity of GaCl3 containing
MCM-41 is higher as compared to that of InCl3 supported catalyst (table 4). Similar results were observed
earlier for In and Ga modied Hb catalysts. The catalytic activity of InCl3 supported on mesoporous SiMCM-41 in the acylation of bulky aromatic compounds
is also explored and the results are presented in table 5.
Catalytic result suggests that the InCl3/Si-MCM-41 also
showed high activity in the acylation of various bulky
aromatic compounds e.g. naphthalene and substituted
naphthalenes in the presence of 1,2-dichloroethane solvent by acyl chlorides (table 5). Importantly, in the cases
of substituted naphthalenes, acylation at the ortho
position relative to that of the para position was found
to be very small indicating a high regio selectivity in the
acylation.
2.2 Catalysis by metal oxide-based solids
Metal oxides in their pure form or in mixtures were
utilized as solid catalysts in various ne chemical

101

S.K. Jana/Friedel-Crafts acylation of aromatics

Table 4
Acidities and benzene benzoylation activities of the mesoporous Si-MCM-41 supported InCl3 and GaCl3 catalysts at 80 C [reaction conditions:
reaction mixture = 145.5 mmol benzene + 8.6 mmol benzoyl chloride + 0.4 g catalyst, reaction temperature = 80 C]
IR peaksa (cm)1)

Catalyst

InCl3 (20 wt%)/Si-MCM-41

GaCl3 (20 wt%)/Si-MCM-41
Si-MCM-41
H.Al-Si-MCM-41
a
b

1st

2nd

1460
1461

1623
1637

Time required for half

the reaction (h)

Reaction induction
periodb (min)
4.9
5.9
No reaction for 2 h
< 1.0% conversion in 5 h

1.6
1.9

TON for half the

reaction (h)1)
7.4
5.0

Pyridine co-ordinated with Lewis acid sites.

Time elapses between the start of reaction and the formation of a benzoylated product.

syntheses processes [47]. They are commercially available and also easily synthesizable. Moreover, they are
generally stable toward moisture and their properties
can be tailored by various post treatments.
So far a few metal oxides based on Fe (III), Zn (II),
Sn (II), Mo (IV) and Cu (II) have been reported for the
acylation of aromatics by benzoyl chloride [1517].
Among the various metal oxide catalysts, Fe (III)
showed the highest catalytic activity in the benzoylation
of benzene and substituted benzene.
Modication of metal oxides by sulfate, tungstate or
molybdate produced strong solid acids, which are
known to catalyze various chemical transformations. It
is reported that sulfated zirconia, sulfated alumina,
sulfated zirconiaalumina, sulfated titaniaalumina,
sulfated iron oxidealumina, tungstated zirconia, tungstated titania, tungstated iron oxide and molybdated

zirconia can eciently catalyze acylation of aromatics

by various acyl halides [1824]. Although the above
catalysts exhibited high activity for the acylation of
activated aromatics but showed low or no activity particularly for non-activated aromatic compounds (e.g.
benzene).
Recently, we observed that non-acidic Ga2O3 and
In2O3 supported on high silica mesoporous Si-MCM-41
showed high catalytic activity in the acylation of benzene and other aromatic compounds by various acyl
chlorides [4446]. Results on the benzoylation of different aromatic compounds at 80 C over the supported
Ga2O3 and/or In2O3 catalysts are presented in tables 6
and 7. Data in table 6 shows that, both the Ga2O3 and
In2O3 supported on mesoporous Si-MCM-41 exhibited
very high benzene benzoylation activity, the supported
In2O3 is; however, more active. Similar results were

Table 5
Catalytic performance of InCl3 (20 wt%)/Si-MCM-41 in the acylation of various aromatics by dierent acyl chlorides [reaction conditions:
reaction mixture = 20 mmol aromatic compound + 11 ml dichloroethane + 8.6 mmol acyl chloride + 0.4 g catalyst, reaction
temperature = 80 C, reaction period = 3 h]
Aromatic compound

Acylating agent

Main producta

Yieldb (%)

C6H5COCl
C6H5COCl
C6H5COCl
C2H5COCl

1-Benzoyl naphthalene
1-Benzoyl-2-methylnaphthalene
1-Benzoyl-2-methoxylnaphthalene
1-Propio-2-methoxylnaphthalene

67
74
88
92

Naphthalene
2-Methyl naphthalene
2-Methoxy naphthalene
2-Methoxy naphthalene
a
b

In case of substituted naphthalenes, the yield of ortho acylated product was very small ( < 8%).
Yield based on acyl chloride.

Table 6
Physico-chemical properties and benzene benzoylation activities of supported Ga2O3 and In2O3 catalysts [reaction conditions: reaction
mixture = 145.5 mmol benzene + 8.6 mmol benzoyl chloride + 0.4 g catalyst, reaction temperature = 80 C]
Catalyst

In2O3(20%)/Si-MCM-41
Ga2O3(20%)/Si-MCM-41
In2O3(20%)/Silica (LS)
Ga2O3(20%)/Silica (HS)
Si-MCM-41
Silica (LS)
a

Surface area
(m2g)1)
846
994
3.1
3.5
1180
0.2

Pyridine chemisorbed
at 400 C (mmolg)1)
0.0
0.0
0.0
0.0
0.0
0.0

Reaction induction
perioda (min)
0.4
0.7
0.9
1.3
No reaction for 2 h
No reaction for 2 h

Time elapses between the start of reaction and the formation of a benzoylated product.

Time required for half

the reaction (h)
4.8
6.1
6.7
8.5

TON for half the

reaction (h)1)
1.6
0.8
1.1
0.6

102

S.K. Jana/Friedel-Crafts acylation of aromatics

observed earlier for Ga and In modied Hb catalysts.

The In2O3 supported on mesoporous Si-MCM-41 also
showed high activity in the benzoylation of various
aromatic compounds in the presence or absence of solvent (table 7). The acylation activity of In2O3/Si-MCM41 largely depends on the types of solvent used in the
reaction (table 7). Among the three dierent solvents
employed for the benzoylation of benzene, the time required for half the reaction were in the following order:
dichloroethane (2.8 h) < acetonitrile (3.2 h) < nheptane (6.5 h). Results suggest that the catalyst showed
higher activity in the presence of polar solvent; although, the catalytic results are not parallelly correlated
with Reichardt ETN polarity parameters (acetonitrile > dichloroethane > n-heptane). It is interesting
to note that, the catalytic activity of In2O3/Si-MCM-41
in the benzene benzoylation reaction under solvent-free
condition is higher as compared to the reaction carried
out in the presence of non-polar solvent; however, it is
lower when compared with the reaction carried out in
the presence in polar solvent. As expected, the activity of
In2O3/Si-MCM-41 is decreased markedly with decreasing In2O3 loading, suggesting the importance of metal
oxide species in the acylation process. Since Ga2O3 and
In2O3 are supported on mesoporous supports, we tried
to explore the use of these catalysts for the acylation of
large size aromatic compounds. The catalytic results of
the acylation of bulky aromatic compounds by benzoyl
chloride over Ga2O3/Si-MCM-41 are presented in
table 8. Above results suggest that Ga2O3/Si-MCM-41
also showed high activity in the acylation of bulky
aromatics, e.g. naphthalene and methyl naphthalene
Table 7
Catalytic performance of In2O3(20 wt%)/Si-MCM-41 in the acylation
of benzene and substituted benzenes by benzoyl chloride [reaction
conditions: reaction mixture = 145.5 mmol aromatic compound + 8.6 mmol benzoyl chloride + 0.4 g catalyst, reaction
temperature = 80 C]
Aromatic
compound

Benzene
Benzenea
Benzeneb
Benzenec

Solvent

No
No
No
Dichloroethane
Benzenec Acetonitrile
Benzenec n-Heptane
Toluene
No
p-Xylene No
Mesitylene No
Anisole
No
a

Main productd

Benzophenone
Benzophenone
Benzophenone
Benzophenone
Benzophenone
Benzophenone
4-Methylbenzophenone
2,5-Dimethylbenzophenone
2,4,6-Trimethylbenzophenone
4-Methoxybenzophenone

Time required
for half the
reaction (h)
4.8
7.6
14.2
2.8
3.2
6.5
3.1
2.5
2.2
1.7

Catalyst In2O3 (10 wt%) / Si-MCM-41.

Catalyst In2O3 (5 wt%) / Si-MCM-41.
c
Reaction mixture = 20 mmol benzene + 11 ml solvent + 8.6 mmol benzoyl chloride + 0.4 g catalyst.
d
In case of substituted benzenes, the yield of ortho acylated product
was very small ( < 10%).
b

Table 8
Catalytic performance of Ga2O3 (20 wt%)/Si-MCM-41 in the acylation
of large aromatic compounds by benzoyl chloride [reaction conditions:
reaction mixture = 20 mmol aromatic compound + 11 ml dichloroethane + 8.6 mmol benzoyl chloride + 0.4 g catalyst, reaction
temperature = 80 C, reaction period = 3 h]
Aromatic compound

p-Xylene
Mesitylene
Naphthalene
2-Methyl
naphthalene
2-Methoxy
naphthalene
a

Main product

Yielda
(%)

2,5-Dimethylbenzophenone
2,4,6-Trimethylbenzophenone
1-Benzoyl naphthalene
1-Benzoyl-2-methylnaphthalene

64
71
54
62

1-Benzoyl-2-methoxylnaphthalene

76

Yield based on acyl chloride.

aorded acyl naphthalene and acyl methyl naphthalene

in very high yields. Moreover, since Ga2O3 and In2O3
are non-acidic nature, it is expected that these solids can
also be employed for the acylations of acid-sensitive
organic compounds. The use of the above catalysts for
acylation of acid-sensitive aromatic compound is under
progress. It is important here to note that the benzoylation activity of the Ga2O3 and In2O3 supported on
acidic support, e.g. Hb, is distinctly higher than that of
the In2O3 and Ga2O3 supported on non-acidic support,
e.g. Si-MCM-41 (tables 2 and 6). This indicates that in
addition to the acidity, if present, the presence of Ga2O3
or In2O3 is very important for showing high activity of
these solid catalysts in the acylation process.
To the best of our knowledge, the example of the use
of heterogeneous basic solids to mediate Friedel-Crafts
acylation of aromatics is scarce. For the rst time we
have successfully explored the possibility of using heterogeneous basic catalyst for the Friedel-Crafts benzoylation reaction [48].
For this purpose, we developed basic Tl2O3 based
solid catalysts by supporting it on various low and high
surface area commonly available catalyst carriers and
used in the liquid-phase Friedel-Crafts acylation of
benzene and substituted benzenes by benzoyl chloride
[48]. The benzoylation results of supported Tl2O3 catalysts at 80 C together with the catalyst characterization
data are presented in table 9. Result shows that, for the
chemically similar supports, that with low surface area
(LS) [viz. zirconia (LS) or silica (LS)] provided a much
more active supported Tl2O3 catalyst as compared to the
Tl2O3 supported on high surface area (HS) catalyst
carrier [viz. zirconia (HS) or Si-MCM-41 (HS)] for the
benzene benzoylation reaction. Although the catalytic
activity Ga2O3 and In2O3 supported on high surface
area mesoporous Si-MCM-41 is found to be even higher
as compared to the catalyst obtained from the low surface area support material in the acylation reaction
under similar experimental conditions (table 6). It is
interesting here to note that, the zirconia (HS)

103

S.K. Jana/Friedel-Crafts acylation of aromatics

Table 9
Physico-chemical properties and benzene benzoylation activities of the supported Tl2O3 (loading of Tl2O3 = 20 wt%) catalysts [reaction
conditions: reaction mixture = 145.5 mmol benzene + 8.6 mmol benzoyl chloride + 0.4 g catalyst, reaction temperature = 80 C]
Catalyst

Tl2O3/Zirconia (LS)
Tl2O3/Zirconia (HS)
Tl2O3/Zirconia (HS)b
Tl2O3/Silica (LS)
Tl2O3/Si-MCM-41 (HS)
Tl2O3/Si-MCM-41 (HS)b
Tl2O3/Si-MCM-41 (HS)c
a
b
c

Color of the
catalyst
Dark grey
Grey
Dark grey
Grey
Very light grey
Light grey
Light grey

Surface area
(m2g)1)
0.3
29
18
0.3
49
28
17

Induction perioda
(min)
9.2
No reaction
11.5
23.7
No reaction
No reaction
No reaction

Time required for

half the reaction (h)

TON for half the

reaction (h)1)

2.6

4.7

3.3
6.2

3.7
2.0

for 2.5 h

for 2.5 h
for 2.5 h
for 2.5 h

Time elapses between the start of reaction and the formation of a benzoylated product.
Tl2O3 loading of 40 wt%.
Tl2O3 loading of 60 wt%.

supported Tl2O3 shows acylation activity only above the

Tl2O3 loading of 20 wt% but the Si-MCM-41 (HS)
supported Tl2O3 does not exhibit any catalytic performance even at the Tl2O3 loading as high as 60 wt%. The
observed strong inuence of various catalyst supports
on the acylation activity of the supported Tl2O3 catalysts suggests dierent extent of interaction between
Tl2O3 and the supports. Strong metal-support interactions are well known in solid-state chemistry and observed in many supported metals; however, the
information on the chemical nature of strong metalsupport interactions is scarce. The low surface area
support is highly sintered macroporous material and
hence have no surface hydroxyl groups; whereas, the
high surface area support is known to have appreciable
amounts of surface hydroxyl groups. In the present case,
the strong Tl2O3-support interactions are mostly due to
the presence of surface hydroxyl groups in the high
surface area support. Since Tl2O3 is basic in nature, it
can interact chemically with the weakly or strongly
acidic surface hydroxyls of the high surface area supports. On the other hand, the low surface area support is
sintered material having no surface hydroxyls and hence
it keeps Tl2O3 unchanged and catalytically active after
supporting. It is very important to note that, thallium
compounds are very toxic in nature and hence Tl2O3
based catalyst should be handle much more carefully.
2.3 Catalysis by clays
Clays are microporous pillared solids possessing
gallery structures and are composed of alternating sheets
and interlayer [49]. They are broadly classied into two
types cationic clay and anionic clay. Cationic clays
consist of crystalline sheets of aluminosilicates that are
negatively charged and the cations e.g. Na+, K+ or
Ca2+ are located in the interlayer between the sheets.
The cations originally present in the cationic clays are
easily replaceable by other cations. Anionic clays are
complementary to cationic clays as the charge on the
layers and the gallery ions are reversed. Hydrotalcite

(i.e. layered double hydroxide) is an important class of

anionic clay, in which the layers are polyhydroxy cations
and the gallery species are hydrated anions. The surface
basicities of hydrotalcites can be tuned easily by
exchanging the anionic species in the interlayer by others; in addition, various kinds of metal cations as potential catalytically active centers can be readily
incorporated into the hydrotalcite framework via their
isomorphic substitution for MgII or AlIII cations at the
octahedral sites of the Brucite-like sheets. Clay materials
with or without modications are reported for a wide
variety of organic transformations [50].
Till date, the literature on the use of clays in the
acylation of aromatics by acyl halide as an acylating
agent is very limited. Cationic clays montmorillonite
K10 and KSF with or without their modications by Fe
(III) and Zn (II) are reported for the acylation of activated aromatics by acyl halides [2528]. Bentonite claysupported polytriuoromethanesulfosiloxane was also
applied for the acylation of highly activated aromatic
compound (ferrocene) with acyl chloride [29]. However,
the use of clay based solid for the acylation of nonactivated aromatics (e.g. benzene) by acyl halide was not
reported in the literature.
We modied a number of cationic clays by supporting InCl3 and GaCl3 from their non-aqueous solution
and used for acylation of benzene [which is dicult to
acylate due to the absence of electron-donating aromatic
ring activating group(s)] [41,51]. The results on acylation
of benzene by benzoyl chloride at 80 C over dierent
clay supported InCl3 and GaCl3 catalyst are presented in
table 10. Result suggests that the support clay itself
shows no catalytic activity in the benzene benzoylation
reaction; however, the catalytic activity is increased
drastically after their modication with InCl3 or GaCl3.
Among InCl3 and GaCl3 supported on the same cationic
clay, the supported InCl3 showed the better acylation
activity. Although, IR spectroscopic data for adsorbed
pyridine on the supported GaCl3 and InCl3 catalysts
indicate that the Lewis acidic character of supported
InCl3 is lower than the supported GaCl3 (table 10). The

104

S.K. Jana/Friedel-Crafts acylation of aromatics

Table 10
Acidities and benzene by benzoylation activities of clay supported InCl3 and GaCl3 (metal chloride loading 20 wt%) catalysts [reaction
conditions: reaction mixture = 145.5 mmol benzene + 8.6 mmol benzoyl chloride + 0.4 g catalyst, reaction temperature = 80 C]
Catalyst

InCl3/mont.-K10
InCl3/mont.-KSF
InCl3/kaoline
GaCl3/mont.-K10
GaCl3/mont.-KSF
GaCl3/kaoline
Supportc
a
b
c

IR peaksa (cm)1)
1st

2nd

1462

1464

1611

1632

Reaction induction
periodb (min)
4.5
5.4
7.7
5.6
6.8
8.5
No reaction for 2 h

Time required for

half the reaction (h)
1.4
2.0
7.9
1.7
2.6
10.4

TON for half

the reaction (h)1)
8.5
6.0
1.5
5.6
3.6
0.9

Pyridine co-ordinated with Lewis acid sites.

Time elapses between the start of reaction and the formation of a benzoylated product.
mont.-K10, mont.-KSF or kaoline

observed higher Lewis acidic character of the supported

GaCl3 is consistent with the higher electro-negativity of
gallium. The similar trend for the other In and Ga
containing catalysts for acylation reactions was
observed earlier. It is found that, the activity of InCl3
supported clay catalyst in the acylation reaction depends
largely on the types of clays. Among the various cationic
clays used for the preparation of InCl3 based catalysts,
montmorillonite-K10 found to be the best support. The
catalytic performance of InCl3/montmorillonite K10 in
the acylation of various alcohols by acyl chlorides is
presented in table 11. Above observations reveal that
the supported InCl3 catalyst (having very low acidity)
can eciently catalyze acylation of a wide range of
alcohols by acyl halides. These results also suggest that
the acylation activity of the supported InCl3 and GaCl3
catalysts depend partially on their acidic character, if
present. However, the concentration of the metal chloride species rather than the strong acidic property of
these catalysts seem to play an important role in the
acylation process.
The example of the use of highly basic anionic clay
based solids to mediate Friedel-Crafts reactions of aromatics is scarce. We reported for the rst time that
MgGa-hydrotalcite possessing very high basicity could
eciently catalyze liquid-phase Friedel-Crafts alkylation
of toluene by benzyl chloride [52]. Additionally, it is

observed that the activity of the hydrotalcite is dramatically increased after its rst use. It is interesting here
to note that, although the fresh MgGa-hydrotalcite does
not show any acylation activity for a long reaction time;
however, the catalyst obtained after benzylation of toluene exhibited high activity in the acylation of aromatics
by acyl chloride [5254]. The reason for abrupt increase
in catalytic activity of MgGa-hydrotalcite after its rst
use in the benzylation is seems to be mostly due to its
surface modication during the reaction. The HCl
formed during the benzylation of aromatics by benzyl
chloride reacts with highly basic hydrotalcite precursor
and transform MgGa-hydrotalcite to highly dispersed
GaCl3 and MgCl2 on MgO, Ga2O3 and MgGa-hydrotalcite. It is important to note that the MgGa-hydrotalcite derived catalyst exhibited good reusability in
addition to its very high activity in the benzylation
reactions.
In order to prepare highly active hydrotalcite derived acylation catalyst, recently we modied MgGahydrotalcite by reacting with gaseous hydrogen chloride before its use in the acylation reaction [55]. Pretreatment of hydrogen chloride to MgGa-hydrotalcite
was performed by bubbling gaseous HCl (20 mol%
HCl in N2) through a mixture containing powered
hydrotalcite and liquid aromatic substrate at 110 C
for 1.0 h followed by ushing with pure N2 in order to

Table 11
Catalytic performance of InCl3/mont.-K10 catalyst in the acylation of various alcohols by dierent acyl chlorides [reaction conditions: reaction
mixture = 20 mmol aromatic alcohol + 11 ml of solvent + 8.6 mmol acyl chloride + 0.1 g catalyst, reaction temperature = 50 C]
Substrate
Benzyl alcohol
Benzyl alcoholb
Benzyl alcohol
Benzyl alcohol
Phenol
4-Nitrophenol
1-Naphthol
2-Naphthaol
a
b

Acylating agent
C6H5COCl
CH3COCl
C2H5COCl
C3H7COCl
C6H5COCl
C6H5COCl
C6H5COCl
C2H5COCl

Yield is based on acyl chloride.

Reaction temperature = 30 C.

Reaction time (h)

1.0
0.7
0.2
0.3
0.3
0.4
2.0
0.5

Main product
Benzyl benzoate
Benzyl acetate
Benzyl propionate
Benzyl butyrate
Phenyl benzoate
4-Nitrophenyl benzoate
1-Naphthyl benzoate
2-Naphthyl benzoate

Yielda (%)
96
92
93
91
95
98
82
87

105

Time elapses between the start of reaction and the formation of a benzoylated product.
HCl vapor passed at 110 C for 1 h.
Obtained after toluene benzylation at 110 C.

0.48
GaCl3, MgCl2, MgO and
MgCO3 (trace)
7.3
Yellowish
Used MgGa-hydrotalcitec

2.3

0.47
GaCl3, MgCl2, MgO,
Hydrotalcite
(trace) and MgCO3 (trace)
7.6
2.8
O-white
HCl-treated
MgGa-hydrotalciteb

9.7

9.4

Pure hydrotalcite

0.00

Toluene
Anisole
Benzene
Toluene
p-Xylene
Mesitylene
Anisole
Toluene
Anisole

No reaction for 5 h
No reaction for 5 h
0.2
0.2
0.1
0.1
0.1
0.1
0.1

141
69
60
53
38
73
40

2.1
4.2
4.9
5.5
7.6
4.0
7.3

TON for half

the reaction
(h)1)
Time required for
half the reaction
(min)
Reaction
induction
perioda (min)
Aromatic
substrate
Surface Cl/(Mg + Ga)
ratio
XRD phases
pH of catalyst
(0.1 g)-water
(20 ml) mixture
Surface
area
(m2g)1)
Color

White

In the Friedel-Crafts acylation of aromatics by acyl

halide over conventional Lewis acidic catalysts, the

MgGa-hydrotalcite

3. Moisture tolerance ability of Ga, In and Tl based novel

solids in the acylation reaction

Catalyst

remove physically adsorbed or absorbed HCl from the

reaction mixture. The results on acylation of various
aromatics over MgGa-hydrotalcite with or without
HCl pretreatment are presented in table 12. Results in
table 12 reveal that the fresh MgGa-hydrotalcite
(without HCl pretreatment) shows no catalytic activity
in the benzoylation by benzoyl chloride of substituted
benzenes even when the reaction was carried over a
period of 5.0 h. However, after HCl pretreatment, the
catalyst is activated for benzoylation reaction, showing
almost no induction period for the acylation reaction.
The benzoylation activity of the HCl pretreated
catalyst (measured in terms of the time required for
half the reaction) for dierent aromatic substrates
are as follows: anisole (t1/2 = 38 min) > mesitylene
(t1/2 = 53 min) > p-xylene (t1/2 = 60 min) > toluene (t1/2 = 69 min) > benzene (t1/2 = 141 min). It is
important here to note that the benzoylation activity
of the HCl pretreated MgGa-hydrotalcite is much higher
than the values observed earlier for Ga2O3/Si-MCM-41
(or Hb) but lower than that for GaCl3/mont.-K10
(tables 2, 10 and 12).
The above results clearly show that the catalytic
activity of the MgGa-hydrotalcite is increased abruptly
after the HCl pretreatment of the hydrotalcite. This is
mostly because of the modication of hydrotalcite, creating catalytically active sites for acylation reactions.
After HCl pretreatment the crystalline phases present in
the catalyst are changed from a single pure hydrotalcite
phase to GaCl3 and MgCl2 on MgO, Ga2O3 (minor) and
hydrotalcite (minor phases). The similar results were also
observed for MgGa-hydrotalcite obtained after benzylation reactions [52]. The minor hydrotalcite phase in the
HCl pretreated catalyst was totally vanished after its use
in the acylation reaction. This is because of its further
reaction with the HCl produced in the benzoylation
reaction. Both the used (in the toluene benzoylation) and
HCl pretreated catalysts show almost identical performance in the toluene benzoylation reaction (table 12).
The acylation activity of our newly developed novel
Ga, In and Tl based solid catalysts are compared with the
commonly used strongly acidic heterogeneous catalysts
Hb, HY, heteropolyacid, Naon, sulfated ZrO2, tungstated ZrO2, molybdated ZrO2 and tungstated Fe2O3 for
their performance in the acylation reaction in table 13.
Results in table 13 suggest that, the Ga, In and Tl based
solids show distinctly higher catalytic performance in the
benzoylation of various aromatic compounds by benzoyl
chloride than the conventionally use strongly acidic heterogeneous catalysts reported in the literature.

Table 12
Physico-chemical properties and acylation performances of fresh, HCl-treated and used MgGa-hydrotalcite in the acylation of benzene and substituted benzenes by benzoyl chloride [reaction
conditions: reaction mixture = 145.5 mmol aromatic substrate + 8.6 mmol benzoyl chloride + 0.4 g catalyst, reaction temperature = 80 C]

S.K. Jana/Friedel-Crafts acylation of aromatics

106

S.K. Jana/Friedel-Crafts acylation of aromatics

Table 13
Comparison of the benzoylation activities of Ga, In and Tl based novel solids with that of the earlier reported heterogeneous catalysts
Catalyst

Tl2O3/Zirconia (LS)
Tl2O3/Silica (LS)
In2O3/Silica (LS)
Ga2O3/Silica (LS)
In2O3/Si-MCM-41
Ga2O3/Si-MCM-41
In2O3/ Hb
Ga2O3/Hb
InCl3/mont.-K10
GaCl3/mont.-K10
HCl pretreated MgGa-hydrotalcite
Hb
Hb
H-mordenite
HY
Sulfated ZrO2
WO3/ZrO2 (or TiO2)
MoO3/ZrO2
WO3/Fe2O3
Zn mont.-K10
H3PW12O40
Cs2.5H0.5PW12O40
Naon

Substrate

Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Benzene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
p-Xylene
p-Xylene
p-Xylene
p-Xylene

Catalyst/C6H5COCl
wt.ratio

0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.33
0.5
1.78
1.78
1.78
0.2
0.05
0.05
0.05

presence of even small amount of moisture in the reaction mixture is found to be harmful for both the catalyst
and the acylating agent. In the presence of water the
activity of Lewis acid-based catalyst drastically lowered
down and moreover the acyl halide undergoes hydrolysis reaction. Because of the above reasons, the acylation reactions over Lewis acid catalyst generally
performed under stringent moisture-free conditions.
However, we observed that Ga, In and Tl based heterogeneous solids can eciently catalyze liquid-phase
Friedel-Crafts acylation of aromatics by acyl chloride
even in the presence of small amount of water in the
reaction system. Results showing the eect of moisture
present in the reaction mixture on the benzene benzoylation over the Ga, In and Tl containing solid catalysts
are presented in table 14. Data in table 14 reveals that
the acylation activity of In2O3 (20 wt%)/Si-MCM-41,
GaCl3 (20 wt%)/mont.-K10 and Tl2O3 (20 wt%)/Zirconia (LS) catalysts was not signicantly changed and
ketone selectivity was also not altered even when the
catalyst was exposed to water vapor for a long time
before its use in the acylation reaction. Moreover, it is
observed that the catalytic activity and ketone selectivity
of In2O3 (20 wt%)/Si-MCM-41 were not changed even
when benzene saturated with water was used for the
benzene benzoylation reaction. However, when both the
catalyst exposed in water vapor and benzene saturated
with water were used in the acylation reaction the

Reaction
temperature
(C)

80
80
80
80
80
80
80
80
80
80
80
80
110
110
110
110
100
100
100
140
140
140
140

Conversion of benzoyl
chloride and reaction
time required
Conversion (%)

Time (h)

50
50
50
50
50
50
50
50
50
50
50
54
83.4
19.5
18.8
50
1920
18
74
35
30
57
48

2.6
6.2
6.7
8.5
4.8
6.1
3.9
5.7
1.4
1.7
2.3
18.0
18.0
18.0
18.0
3.2
3.0
3.0
3.0
2.0
2.0
2.0
2.0

Ref.

Table
Table
Table
Table
Table
Table
Table
Table
Table
Table
Table
[12]
[10]
[10]
[10]
[20]
[21]
[21]
[21]
[28]
[28]
[28]
[28]

9
9
6
6
6
6
2
2
10
10
12

catalyst was found to be slightly more active for the

conversion of acylating agent but the ketone selectivity
was signicantly reduced. The observed increase in the
rate of benzoyl chloride conversion over In2O3/SiMCM-41 in the presence of appreciable amounts of
water in the reaction mixture is mainly due to the
hydrolysis of acylating agent. The above facts suggest
that, although the catalytic activity of Ga, In and Tl
based solids in the acylation reaction was not changed
signicantly but the ketone selectivity was remarkably
reduced as a result of the hydrolysis of acyl halide due to
the presence of large amount of water in the reaction
system.

4. Reusability/stability of the catalysts

The reuse of Ga, In and Tl containing solid catalysts
in the acylation was studied one or more times after the
batch run. The catalyst was reused after removing the
supernatant liquid reaction mixture, while retaining the
catalyst in the reactor and avoiding the removal of
catalyst ne particles. Table 15 shows the result of reuse
of In2O3 (20 wt%)/Si-MCM-41, HCl-treated MgGahydrotalcite and Tl2O3 (20 wt%)/Zirconia (LS) catalysts
in the benzene benzoylation reaction. Result indicates
that the catalytic activities of the above solids are decreased for their subsequent reuse in the acylation

107

S.K. Jana/Friedel-Crafts acylation of aromatics

Table 14
Results on eect of moisture in the catalyst and/or substrate on the benzene benzoylation performances of Ga, In and Tl based solids [reaction
conditions: reaction mixture = 145.5 mmol moisture-free benzene + 8.6 mmol benzoyl chloride + 0.4 g catalyst, reaction temperature = 80 C]
Catalyst

In2O3 (20%)/Si-MCM-41

Catalyst pretreatment

Quality of
benzene used

Dried
Pretreated with water vapors
Dried

Dry
Dry
Saturated
with water
Saturated
with water
Dry
Dry
Dry
Dry

Pretreated with water vapors

GaCl3 (20 wt%)/mont.-K10
Tl2O3(20 wt%)/Zirconia (LS)
a
b

Dried
Pretreated with water vapors
Dried
Pretreated with water vapors

Induction perioda
(min)

Time required
for half the
reaction (h)

Selectivity for
benzophenoneb
(%)

0.4
0.2
0.1

4.8
4.7
4.7

98
98
96

0.1

4.1

87

5.6
4.1
9.2
3.0

1.7
1.6
2.6
2.5

97
94
98
96

Time elapses between the start of reaction and the formation of a benzoylated product.
Selectivity based on benzoyl chloride.

Table 15
Results on the reuse of In2O3(20 wt%)/Si-MCM-41, HCl pretreated
MgGa-hydrotalcite and Tl2O3(20 wt%)/Zirconia (LS) in the benzene
benzoylation reaction [reaction conditions: reaction mixture = 145.5 mmol benzene + 8.6 mmol benzoyl chloride + 0.4 g
catalyst, reaction temperature = 80 C]
Fresh/reused
catalyst

Induction
perioda
(min)

Time required
for half the
reaction (h)

Catalyst: In2O3/Si-MCM-41
Fresh
0.4
4.8
First reuse
0.1
5.9
Catalyst: HCl pretreated MgGa-hydrotalcite
Fresh
0.2
2.4
First reuse
0.1
3.3
Catalyst: Tl2O3/Zirconia (LS)
Fresh
9.2
2.6
First reuse
1.1
3.1

Selectivity for
benzophenoneb
(%)

98
97
96
97
97
98

Time elapses between the start of reaction and the formation of a

benzoylated product.
b
Selectivity based on benzoyl chloride.

reaction. The decrease in catalytic activity of Ga, In and

Tl based solids seems to be mostly because of the formation of strong complex between the product ketone
and the metal chloride species in the catalyst. This is
assumed because the formation of strong complex between the ketone and metal oxide species is not so easy
and moreover the presence of metal chloride species in
the used In2O3/Si-MCM-41 and Tl2O3/Zirconia (LS)
catalysts were observed. The decrease in catalytic
activity of oxide-based catalyst seems to be due to its
partial transformation into the chloride species by the
reaction with evolved HCl during acylation reaction.
The reason for decrease in catalytic activity due to pore
blocking is excluded since most of our developed catalysts contain macropore and mesopore and hence dont
have a chance to face the pore restriction during
reaction.

5. Proposed reaction mechanism for the acylation over

Ga, In and Tl containing solid catalysts
The high acylation activity of Ga or In modied Hb
zeolite as compared to the highly acidic Hb is attributed
to the presence of non-framework Ga- or In-oxide species present in the catalyst in combination with the
zeolitic protons. The non-framework metal oxide species
are known for their redox properties, which are expected
to play an important role in activating the acylating
agent in addition to its activation by the zeolitic protonic acid sites during the acylation process. However,
in case of the Ga-oxide (or chloride) or In-oxide (or
chloride) supported on non-acidic inert catalyst carrier
and basic Tl2O3 based solid, because of the absence of
acidic property of the catalysts the benzoylation reaction
over these redox metal containing solids are, therefore,
seems proceed only through the redox mechanism. It is
interesting to note that, when compared the catalytic
activity of Ga, In and Tl oxides supported on same low
surface area support [e.g. silica (LS)], the supported
Tl2O3 shows high activity than the supported Ga2O3 or
In2O3 catalyst for the benzene benzoylation reaction
under similar experimental conditions (tables 6 and 9).
Although, among the catalysts the acidity of Tl2O3/Silica (LS) is the lowest (not shown). Moreover, the order
for the benzoylation activity of the Ga, In and Tl containing oxide-based catalysts supported on a chemically
similar inert catalyst carrier [e.g. silica (LS)] is quite
similar to that for the redox potential of the metal in the
catalysts [E (Tl+3/Tl+1) = + 2.06 V > E (In+3/
In+1) = E (Ga3+/Ga+1) = ) 0.44 V]. The above
facts indicate a close relationship between the redox
properties and the catalytic activities of the Ga-, In- and
Tl-containing solid catalysts, in addition to the acidity
function, if present. Based on the above observations,
following plausible mechanism for the acylation reactions over these solid catalysts are proposed.

108

S.K. Jana/Friedel-Crafts acylation of aromatics

Activation of acyl chloride forming R-CO+ carbocation

R--CO--Cl H Q ! R--CO Q HCl

2R--CO--Cl M3 ! R--CO--Cl M1

R--CO--Cl ! R--CO 2Cl

M1 2Cl ! M3 2Cl

4
)

[RCOCl = acyl
chloride,
H Q = zeolite,
M = Ga, In or Tl]
Reaction between acyl carbocation and aromatic
substrate
H
(Z) p

+ R-CO

pared with the strongly acidic solid catalysts reported

earlier. The Ga, In and Tl based solid catalysts also
preserve their high activity in the acylation reaction even
in the presence of small amount of moisture in the
reaction mixture, which is of great practical importance.
Since the catalytic activities of our newly developed Ga,
In and Tl containing solids are largely depends on their
redox properties and moreover, their oxides are nonacidic or basic in nature, the catalytic activity of these
solids can be explored in the acylation of acid-sensitive
aromatic compounds. The reusability of the Ga, In and
Tl based catalysts can be improved by chemically anchored them onto the solid support and avoided the
presence of metal chloride and/or oxide species in the
catalyst, if possible. Recently, we succeeded to heterogenize Ga by control grafting of GaCl3 with surface hydroxyls of mesoporous silica SBA-15 material and
observed its much better reusability in the acylation
reaction as compared to the supported catalysts [56].

H
+

(Z) p

CO-R

- H+

CO-R
(Z) p

Acknowledgements
Author is very grateful to Professor T. Tatsumi of
Tokyo Institute of Technology, Japan and Dr. V. R.
Choudhary of National Chemical Laboratory, India for
their constant help and encouragement.

(5)

References
The acyl carbocation, formed by the above reactions
[steps (1)(3)] can attack the aromatic substrate leading
to the formation of the acylated product as shown in
step (5).
The acylation activity of the highly acidic Hb zeolite
is much lower than that of their Ga- or In-modied form
probably because of the absence of the redox reactions
[according to steps (2)(4)]. The activities are also lower
in the case when the In2O3 or Ga2O3 are supported on a
non-acidic support (such as high silica mesoporous
MCM-41) as compared to the acidic support (e.g. Hb
zeolite), because of the absence of zeolitic protons and
consequently the absence of reaction (1). The above
redox processes may; however, be considered as a
speculative one. A further detailed investigation is required to conrm the mechanistic pathways.

6. Conclusions and future prospects

Friedel-Crafts type acylation of aromatics over Ga,
In and Tl based novel heterogeneous solid catalysts
ranging from acidic to basic types is described for the
rst time based on their redox properties in combination
with their acidities, if present. The acylation activity of
the above solids is found to be even higher when com-

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