Synthesis and Reactivity in Inorganic, Metal-Organic and Nano-Metal Chemistry, 36:321–324, 2006
Copyright # 2006 Taylor & Francis Group, LLC
ISSN: 0094-5714 print/1532-2440 online
DOI: 10.1080/15533170600651389
Titanium Dioxide-Mediated Friedel –Crafts Acylation of
Aromatic Compounds in Solvent-Free Condition under
Microwave Irradiation
Mohamed Afzal Pasha, Krishnappa Manjula, and
Vaderapura Puttaramegowda Jayashankara
Department of Studies in Chemistry, Central College Campus, Bangalore University, Bangalore, India
Friedel– Crafts acylation of different arenes was carried out in
the presence of titanium dioxide under microwave irradiation in
solvent-free condition. Activated substrates undergo acylation
predominantly at the para-position. An efficient, simple, selective
acylation reaction affords good yield of the products and the
catalyst could be easily recovered and recycled.
Keywords Friedel-Crafts acylation, arenes, acid chlorides, TiO2,
microwave irradiation
INTRODUCTION
The Friedel – Crafts acylation of aromatic compounds is one
of the most established and useful reactions.[1] Used in a wide
variety of fields including pharmaceuticals, fragrances,
polymers, agrochemicals and in the most fundamental C – C
bond forming reactions.[2] The classical Friedel – Crafts acyla-
tion reaction is carried out by using AlCl3.[3,4] The Lewis acid
(AlCl3 or FeCl3) promoted reactions have some limitations,
such as the requirement of more than stoichiometric amount
of the Lewis acid and treatment of the AlCl3 residue after the
reactions. To minimize this problem, catalytic Friedel – Crafts
acylation was achieved by various methods developed
with methane sulfonic acid,[5] perfluorinated sulfonic
acid resin (Nafion – H),[6] HZSM – 5 Zeolites,[7] heteropoly
salt Cs2.5H0.5PW12O40,[8] AIPW12O40,[9] Metal-Cation
(Mþ2Mont),[10] polymer-supported aluminum chloride,[11]
alumina,[12] triflates like Bi(OTf)3 or Sc(OTf )3,[13]
Ln(OTf)3[14] and Yb(OTf)3.[15] Recently, bismuth derivatives
such as (þ)-Bi(OTf)3 or BiOCl or Bi2O3 in the presence of
ionic liquid-[emim][NTf2],[16] metal and metal oxide like
Received 3 December 2005; accepted 16 January 2006.
Address correspondence to Mohamed Afzal Pasha, Department of
Studies in Chemistry, Central College Campus, Bangalore University,
Bangalore 560 001, India. E-mail: m_af_pasha@yahoo.co.in
321
Zn[17] and ZnO.[18] The catalytic Friedel – Crafts acylation
reactions have their own advantages and limitations, for
example, higher selectivity, easier work-up and environmental
safety are some of the advantages. Disadvantages are use of
excess acid catalyst, unsatisfactory yields, cumbersome meth-
odologies, flammability or risk of explosion of the reagents
and cost of the reagents. Thus, the search for new catalysts
and methods is still of practical importance.
Microwaves, on the other hand, accelerate the chemical
reactions in solvents as well as under solvent-free conditions,
and have witnessed an explosive growth. Microwave
irradiation often leads to shorter reaction time, increased
yields and easier work-up matching with “green chemistry”
protocols. The availability of several publications in the
literature clearly indicates the impact of microwave-assisted
reactions in organic synthesis.[19,20]
To promote the Friedel – Crafts acylation, reaction of
aromatic compounds with acid chloride, we have used TiO2,
and the corresponding acylated product is obtained in high
yields under microwave irradiation and solvent-free conditions
as shown in Scheme 1.
RESULTS AND DISCUSSION
In our laboratory we have shown that reduction of different
functional groups using metals/metal salts and/or ammonium
salts is possible, and simple metals such as Al, Zn, Sn, and Sb
can replace expensive and complex reducing agents for
reduction under different reaction conditions.[21 – 25] Now, our
interest is in the use of metal oxides in conjunction with
microwave irradiation.
Recently we have reported synthesis of 3,4-dihydropyrimi-
din-2(1H )-ones/thiones using catalytic amount of ZnCl2 via
Biginelli reaction under microwave irradiation.[26] In this
paper we report a simple, efficient and selective method for
preparation of aromatic ketones by solvent-free Friedel –
Crafts acylation reaction of aromatic compound with benzoyl
chloride and acetyl chloride in the presence of TiO2 under
322 M. A. PASHA ET AL.

Out of the three selected catalysts, TiO2, which is non-toxic,

inexpensive and commercially available, has been used earlier
in a one-step Beckmann rearrangement of aldehydes and
ketones in solvent-free conditions.[27] We found it to have a
remarkable activity for the Friedel-Crafts acylation. The
results of Friedel – Crafts acylation of aromatic compounds cat-
SCH. 1.
alysed by TiO2 under microwave irradiation are presented in
Table 2. Here, it is clear that aromatic compounds react very
microwave irradiation. To find a suitable catalyst, we worked rapidly (within 20 –50 sec) to give ketones. The reactions are
with three different metal oxides, namely: TiO2, CdO, and clean, and easy acylation of unactivated benzenes such as
CuO under solvent-free conditions and found that metal chlorobenzene also takes place, affording the corresponding
oxide can promote the Friedel – Crafts acylation of aromatic aromatic ketone in acceptable yields (Table 2, entries 2 and 8).
compounds affording the corresponding acylated products in Acylation occurs exclusively at the position para to group
satisfactory yields, as shown in Table 1. presented in the arene. We report here only the major isomer,
which has been isolated by column chromatography.
We have examined the recovery and reuse of the catalyst
TABLE 1 on the benzoylation of toluene to get 4-methylbenzophenone
Friedel – Crafts acylation of chlorobenzene with benzoyl and found that the yields of the product in the second and
chloride using different metal oxide under third use of the catalyst were almost same as that in the first
microwave irradiation use. In every case, .90% of TiO2 was recovered by filtration,
washing with water and drying at 120 8C (Table 3).
Reaction
temperature Time Yield
Entry Metal oxide ( 8C) (sec) (%) EXPERIMENTAL
All aromatic compounds, acid chlorides and metal oxides
1 TiO2 100– 103 20 70
were purchased from BDH/MERCK and all the solvents
2 CdO 105– 109 30 65
were distilled before use. All the reactions were carried out
3 CuO 110– 113 35 60
using a conventional (unmodified) household microwave

TABLE 2
Friedel-Crafts acylation of substituted arenes with benzoyl chloride and acetyl chloride in the presence of TiO2
under microwave irradiation
Reaction Time Yield m.p b.p ( 8C)
Entry Substrate Product temp ( 8C)1 (sec) (%) Found/reported

With benzoyl chloride

1 Benzene Benzophenone 68 25 72 46– 48/48 –49b
2 Chlorobenzene 4-Chlorobenzophenone 103 20 70 74– 76/75 –77b
3 Toluene 4-Methylbenzophenone 80 20 68 56– 58/56.5 –57a
4 2-Xylene 3,4-Dimethylbenzophenone 63 50 69 46– 47/45 – 47a
5 Naphthalene 2-Benzoylnaphthalen 70 25 65 80– 82/82c
6 1,2-Dichlorobenzene 3,4-Dichlorobenzophenone 60 30 65 103/101– 104b
With acetyl chloride
7 Benzene Acetophenone 68 35 68 201– 202/202a
8 Chlorobenzene 4-Chloroacetophenone 70 35 65 232/230– 232b
9 Naphthalene 2-Acetonaphthanone 47 25 60 54– 56/56c
10 Toluene 4-Methylacetophenone 45 30 65 224– 226/226a
1
Reaction temperature was measured by immersing a glass thermometer into the reaction mixture immediately after exposure to microwave
irradiation.
a
Aldrich: Handbook of Fine Chemicals and Laboratory Equipment, Sigma-Aldrich Corporation, Mahadevapura, Bangalore, India, 2001.
2000– 2001.
b
Lancaster, 2002– 2003: Research Chemicals, Lancaster Synthesis Ltd., Lancashire, England, 2003.
c
Ref.[17]
 FRIEDEL CRAFTS ACYLATION OF AROMATIC COMPOUNDS IN SOLVENT-FREE CONDITIONS
TABLE 3
Repeated use of TiO2 for acylation of
toluene with benzoyl chloride under
microwave irradiation
Number Time Yield Recovery
of uses (sec) (%) of TiO2
1 20 68 95
2 30 64 90
3 40 60 88
oven (LG, Little Cheff, 230 V, 50 Hz). Reactions were
monitored on TLC by comparison with authentic samples.
Melting points were taken in open capillaries using paraffin
bath and are uncorrected.[28] Yields refer to the isolated
yields of the products after purification by silica gel chromato-
graphy. The IR spectra of the products were recorded on a
Nicolet 400 D FT-IR spectrophotometer. H1 NMR spectra
were recorded on a 400 MHz Bruker instrument. The
chemical shift values (d ppm) reported are relative to TMS in
CDCl3 as solvent.
General Procedure for Conversion of Aromatic
Compounds to Aromatic Ketones under
Microwave Irradiation
A mixture of benzene (0.078 g, 1 mmol) and TiO2 (0.039 g,
0.5 mmol) was taken into a Pyrex cylindrical tube; benzoyl
chloride (0.140 g, 1 mmol) was added, homogenized and
irradiated in a commercial microwave oven (320 W). At the
end of irradiation (25 sec), the mixture was cooled to room
temperature and extracted with diethyl ether. The organic
layer was dried over sodium sulphate, and the solvent
was removed under vacuum. The crude product was
subjected to silica gel column chromatography using 5%
EtOAc in light petroleum ether as eluent to get benzophenone
(0.13 g).
CONCLUSION
The present microwave irradiation procedure provides an
efficient and very simple method for Friedel – Crafts acylation
of aromatic compounds using non-toxic and inexpensive
TiO2 powder. This catalytic system is expected to contribute
to the development of more benign acylation of aromatics
with acid chlorides.
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