Catalysis Communications 3 (2002) 363–367

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Fe3þ-montmorillonite: A bifunctional catalyst for one pot

Friedel–Crafts alkylation of arenes with alcohols
Boyapati M. Choudary *, Bhavnari P.C. Rao, Naidu S. Chowdari,
Mannepalli L. Kantam
Inorganic Chemistry Division, Indian Institute of Chemical Technology, Hyderabad 500 007, India
Received 12 February 2002; received in revised form 12 June 2002; accepted 12 June 2002

Abstract

Fe3þ -montmorillonite catalyzes one pot Friedel–Crafts alkylation of arenes using alcohols and catalytic amount of
p-toluenesulfonic acid (TsOH) or methanesulfonic acid (MsOH) for the first time. Ó 2002 Elsevier Science B.V. All
rights reserved.

Keywords: Fe3þ -montmorillonite; One pot reaction; Sulfonylation; Friedel–Crafts alkylation

1. Introduction complex structures of fascinating stereochemistry

The development of cutting-edge and cleaner
processes is of topical interest to meet global
competition and conform stringent environmental
specification. The use of solid acids to replace
waste generating soluble Lewis acids for the al-
kylation of arenes and acylation of activated are-
nes facilitates improved procedures. Improving the
efficiency of organic processes in terms of lowering
energy consumption and the process time and
minimizing the use of equipment, chemicals and
generation of waste is a major goal in synthetic
chemistry. Performing the multistep synthesis in
one pot, prevalent in biosystems, wherein the
*
Corresponding author. Tel.: +91-40-7193510; fax: +91-40-
7160921.
E-mail address: choudary@iict.ap.nic.in (B.M. Choudary).
are constructed from a very small molecule, is an
attractive strategy to achieve this goal [1].
Friedel–Crafts alkylation is a very important
tool for introducing alkyl substituents into aromatic
ring system [2]. In general this type of reaction is
carried out by using alkyl halides [3], allylic or
benzylic alcohols [4], alkyl sulfonates [5], etc. as al-
kylating agents in the presence of Lewis acids [6]
such as AlCl3 ; FeCl3 ; ZnCl2 ; SbCl5 ; SnCl4 ; BF3 ;
Ag ðOTfÞ3 ; BiðOTfÞ3 ; ScðOTfÞ3 and Bronsted
acids such as polyphosphoric acid [7] or triflicacid
[8]. Further the use of various alkylating agents
generates the acid byproducts. Besides this, the use
of alkyl halides and alkyl sulfonates requires addi-
tional unit operations for their preparations. All of
these catalysts have the disadvantages such as gen-
eration of large amount of waste, inability to recy-
cle, and moisture sensitive. The alcohols are also

1566-7367/02/$ - see front matter Ó 2002 Elsevier Science B.V. All rights reserved.
PII: S 1 5 6 6 - 7 3 6 7 ( 0 2 ) 0 0 1 4 3 - 7
364 B.M. Choudary et al. / Catalysis Communications 3 (2002) 363–367
employed as alkylating agents in presence of clay
but this reaction requires high temperatures (350–
400 °C) and pressure to obtain optimum yields
(18.8–38.8%) [9]. Therefore, the development of
more economical process for alkylation of aromat-
ics using alcohols is highly desirable.
The use of clays as catalysts and catalyst sup-
ports has received considerable attention recently
[10,11]. Expandable layer lattice clays such as
montmorillonites have magnetic field acidity (H0 )
values between 1.5 and )3 and their acidities may
be tuned further by metal ion exchange with the
introduction of large number of Lewis acidic sites.
Recently we developed a new method for sulf-
onylation of alcohols using p-toluenesulfonic acid
in presence of metal-exchanged montmorillonite
catalyst [12]. Here we report Fe3þ -montmorillonite
catalyzed one pot Friedel–Crafts alkylation of
aromatics using alcohols and catalytic amount of
p-toluenesulfonic acid (TsOH) or methanesulfonic
acid (MsOH) for the first time. In these reactions
water is the only byproduct.
2. Experimental
2.1. Preparation of catalyst
To a 1L aqueous solution of FeCl3  6H2 O
ð1:0 MÞ; 80 g of K10-montmorillonite was added.
Stirring was maintained for 16–30 h in order to
saturate the exchange capacity of K10-montmo-
rillonite. The clay suspension was centrifuged and
the supernatant solution was discarded. Washing
cycles were repeated until disappearance of Cl
ions from the discarded water. The clay was dried
overnight in an oven at 120 °C and finely ground
in a mortar. The metal content of Fe3þ -montmo-
rillonite catalyst was analyzed according to Vo-
gel’s procedure and found to be 6.3%. Acidic sites
of Fe3þ -montmorillonite were estimated by the
temperature-programmed desorption of ammonia
gas (NH3 -TPD) analysis and was found to be
1.029 mmol/g. Specific surface area of the Fe3þ -
montmorillonite is calculated from BET nitrogen
isotherms determined at )196 °C (micromeritics
ASAP 2000) on samples degassed at 250 °C for 12
h before the experiment and found to be 212 m2 /g.
2.2. Preparation of alkylated aromatic compounds
To a solution of alcohol (2 mmol), toluene (2
mmol) and p-toluenesulfonic acid/methanesulfonic
acid (0.2 mmol) in 1,2-dichloroethane (10 ml) was
added Fe3þ -montmorillonite (0.05 g) in a two
necked flask equipped with a Dean–Stark appa-
ratus. The reaction was maintained at reflux tem-
perature. After completion of the reaction
(monitored by TLC), the reaction mixture was
cooled and water was added. Then the catalyst was
filtered and washed with dichloromethane. The
organic layer was dried over anhydrous Na2 SO4
and evaporated under reduced pressure. The crude
product was purified by column chromatography
to afford pure alkyl substituted aromatic com-
pound.
A representative example. Entry 2, Methyl
Phenyl cyclopentane: 1 H NMR (200 MHz,
CDCl3 Þ d, 1.50–1.85 (6H, m), 1.95–2.07 (2H, m),
2.34 (3H, s, p-Me), 2.30 (3H, s, o-Me), 2.94 (1H, tt,
p-CH), 3.18 (1H, tt, o-CH), 6.95–7.23 (4H, m)
identical to the reported values [5b]. The rest of the
products were characterised similarly.
3. Results and discussion
First we employed the Fe3þ -montmorillonite
for Friedel–Crafts alkylation of aromatics using
cyclopentyl methanesulfonate as an alkylating
agent in 1,2-dichloroethane under reflux for 3 h
and obtained cyclopentyltoluene in quantitative
yield. The use of cyclopentanol as alkylating agent
under these conditions gives a nonselective reac-
tion and the product distribution is cyclopentyl-
toluenes (30%), cyclopentene (10%) and
dicyclopentyl ether (60%). The introduction of
MsOH (10 mol%) in to the system afforded the
alkylated product selectively in 93% yield. When
MsOH (10 mol%) is employed in the absence of
 B.M. Choudary et al. / Catalysis Communications 3 (2002) 363–367 365

Fe3þ -montmorillonite, no product is observed.
Next we investigated various aromatics for Fri-
edel–Crafts alkylation using alcohols and catalytic
amount of TsOH or MsOH. The aromatics such as
benzene, tolune, o-xylene, p-xylene, mesitylene and
anisole were alkylated using cyclohexanol and
cyclopentanol with excellent yields. The results are
summarized in Table 1.
Formation of cyclohexyl or cyclopentyl sub-
stituted aromatic compounds by in situ genera-
tion of sulfonic ester is faster when MsOH is used
than the TsOH. The reactions are faster with
cyclopentanol compared to cyclohexanol. This
activity profile may be influenced by steric fac-
tors. More interestingly in case of toluene, alky-
lated products are formed with high para
selectivity. The alkylation of toluene with cylo-
pentanol afforded the cyclopentyltoluenes with
62% para selectivity (ortho:para ¼ 38:62), when
compared to ScðOTfÞ3 catalyzed alkylation with
cyclopentyl methanesulfonate that gives only 50%
para selectivity [5a]. Further cyclohexylation of
toluene with cyclohexanol afforded the cyclohexyl
toluenes in quantitative yield and with 70% par-
aselectivity (ortho:para ¼ 30:70) for 3 h, in
contrast to the TsOH catalyzed cyclohexylation
of toluene with cyclohexyl p-toluenesulfonate,
where cyclohexyl toluenes are formed after 18 h
in the ratio of o:m:p ¼ 28:18:54 [5b]. It is sig-
nificant to note that in our system, no meta iso-
mer is observed and the higher para selectivity is
obtained when compared to the earlier reports.
This may be attributed to the shape selective
nature of the clays. The yields are higher (94%)
and the reaction times are shorter (3h) in one pot
reaction, compared to the overall yield (82%)
obtained and the time required (7h) in the inde-
pendent reactions conducted with Fe3þ -montmo-
rillonite separately. Further the stoichiometric
amount of sulfonic acid required for the prepa-
ration of alkyl sulfonate is minimised by gener-
ating sulfonate in situ with catalytic amount of
sulfonic acid. The sulfonic acid is recovered from
aqueous phase and reused without significant loss
of activity. The catalyst is also recovered by
simple filtration and reused for five cycles for
alkylation of benzene with cyclopentanol and
there was no loss in activity (Table1).
The use of bifunctional catalyst in place of a
mixture of two homogeneous catalysts simplifies
the catalyst recovery and purification of the prod-
ucts. Moreover, conducting the two reactions
simultaneously in one pot avoids isolation and
purification of intermediate sulfonate esters and
thus lowers the equipment inventory, process time,
waste generation, solvent and energy consumption.

Table 1
Fe3þ -montmorillonite catalyzed one pot Friedel–Crafts alkylation of arenes using alcoholsa
Arene Alcohol TsOH MsOH
b
Time (h) Yield (%) Time (h) Yield (%)
Benzene Cyclohexanol 14 90 3 91
Cyclopentanol 12 92 2 95, 94c
Toluene Cyclohexanol 12 92 (30:70) 3 94 (38:62)
Cyclopentanol 10 90 (45:55) 3 93 (38:62)
o-Xylene Cyclohexanol 30 85 8 92
Cyclopentanol 30 93 (66:34) 6 95 (55:45)
p-Xylene Cyclohexanol 41 91 24 94
Cyclopentanol 20 89 6 92
Mestilene Cyclohexanol 48 85 4 88
Cyclopentanol 30 90 3 92
Anisole Cyclohexanol 60 95 (41:59) 5 95 (69:31)
Cyclopentanol 50 95 (40:60) 4 95 (75:25)
a
The catalyst (50 mg), alcohol (2 mmol), arene (2 mmol) and RSO3 H (0.2 mmol) in 1,2-dichloroethane (10 mL) were stirred under
reflux.
b
Values in parenthesis refers to the o-, p-isomers of crude products analyzed by 200 MHz 1 H NMR.
c
Isolated yield of the fifth cycle.
366 B.M. Choudary et al. / Catalysis Communications 3 (2002) 363–367

Acknowledgements

B.P.C.R and N.S.C. thank the Department of

Science and Technology and Council of Scientific
and Industrial Research, India, for research fel-
lowships.

References
Scheme 1. A plausible mechanism for Fe3þ -montmorillonite
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Most importantly the byproduct formed in this
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Crafts alkylation of aromatic nucleus appears to
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