ELSEVTER

Applied Catalysis A: General 132

( 1995) 141-155

Characterization of clay-based K catalysts and their

application in Friedel-Crafts alkylation of aromatics
Tivadar Cseri a,b, Sfmdor B6kAssy a, Fraqois Figueras b,*,
Eleonbra Cseke , Louis-Charles de Menorval , Roger Dutartre
&
Technical
Institut

Universi&

of Budapest,

Department

ojOrganic

Chemica/

Technology,

de Recherches SW la Catalyze du CNRS, 2 Avenue Albert Eimtein

L&oratoire

de Matdriaux

Catalytiques

et Catalyse erl C/like

de 1Ecole Normals,

Organique,

340.53 Montpellier

1521 Budapest, Hungu)

69626, Villeurhanne

Cedeu. France

URA 4/K du CNRS, ENSCM, 8 rue

Cedex, France

Received 20 April 1995: revised 27 June 1995; accepted 27 July 1995

Abstract
Toluene was alkylated with benzyl chloride and benzyl alcohol using a series of clays (KSF, KSF/
0, KO, KPI 0, KlO, KS from Siid Chemie) obtained by treating a bavarian bentonite by different acids
and a Hungarian bentonite (Mid) as catalysts in a batch reactor. The catalysts were characterized by
chemical analysis, thermal analysis, nitrogen adsorption, solid state nuclear magnetic resonance, Xray diffraction. The acidity of these solids was determined by infrared spectroscopy using pyridine as
molecular probe. The structure. specific surface area, and distribution of Lewis/Br@nsted acidity of
these clays can be changed to a great extent by acidic or thermal treatment. The rate of alkylation is
related to BrGnsted acidity when the substrate is benzyl alcohol. When benzyl chloride is used as
alkylating agent, the Fe+ content of the clay controls the activity, and iron containing clays show
high activities in spite of their low Lewis acidities.
Keywords:

Aromatics; Alkylation: K catalysts; Acidic clays; Brensted acidity; Fe

1. Introduction
Solid acids offer many advantages by their nature, over soluble counterparts such
as aluminium chloride and hydrogen fluoride. The substitution of liquid acids by
solids as catalysts for organic synthesis offers a potential for superior effectiveness
and environmental integrity. However the origin of their activity is generally poorly
understood. Although they differ in structure from liquid acids, solid acid catalysts
* Corresponding author. Tel. ( + 33) 72445300, fax. ( + 33) 72445300.
0926-860X/95/$09.50

0 1995

SSDIO926-860X(95)00158-1

Elsevier Science B.V. All rights reserved

142

T. Cseri et al. /Applied

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132 (1995) 141-155

work by the same principle. Clays have been proposed as suitable catalysts for this
purpose [ l-31. Friedel-Crafts alkylation is one of the most important reactions in
synthetic and industrial organic chemistry, thus an interesting model. The alkylation
of toluene by benzyl chloride or benzyl alcohol is interesting for the preparation of
substitutes of polychlorobenzenes
used as dielectrics. These reactions are usually
catalysed by Lewis acids in liquid phase [ 41 in homogeneous phase and an industrial process is based on FeCl, [ 51.
In heterogeneous catalysis, zeolites [6] , sulfated zirconia [7] and clays
exchanged by metallic cations [8-l 1 ] have been described. Particulary good results
have been obtained using as catalyst a zinc chloride impregnated on KlO montmorillonite, called clayzic [ 12-161. Clark et al. [ 171 recently reviewed the work
published on clays impregnated by zinc chloride, and activated at low temperature
(T < 573 K) . K10 activated under these conditions was reported to be non-acidic,
and the catalytic activity of clayzic for the reaction of benzyl chloride on aromatics
was then ascribed to Zn2+ cations.
Using a dealuminated protonic zeolite (HY with a Si/Al ratio of 20) the use of
Hammett relationships gave results in favour of an ionic mechanism [ 61. However
the rate on zeolites is limited by diffusion because of the microporosity and no
relationship could be established between the acidity of different zeolites and the
catalytic properties. Using exchanged clays, Laszlo and Mathy [ 91 found no relation between the activity of the exchanged clays and the properties of the same
chlorides used as Lewis acids in solution. Unfortunately the acid properties of these
solids were not determined, and it is then impossible to conclude on a possible
change of mechanism. Yadav et al. [7] investigated the alkylation of toluene by
benzyl chloride on sulfated zirconia, which is usually considered as a very strong
Lewis acid, and reported a surprisingly low activity compared to other catalysts.
We have recently investigated this type of samples for their acidity and catalytic
properties [ 18-2 I]. The nature of the acid sites can be changed to a great extent
by changing the cations exchanged into the clay and by the thermal pretreatment.
Using Diels-Alder synthesis as model reaction, results consistent with those
obtained from the determination of acidities were obtained: calcination of the clay
induced an increase of Lewis acidity and a parallel increase of activity. On the clays
calcined at 773 K, and then converted to Lewis acids, the rate of the Diels-Alder
addition of cyclopentadiene on methylacrylate was proportional to the number of
acid sites [ 211.
Recently were results reported that were obtained with clays exchanged by
different cations on alkylation of anisole with dienes [ 221. The Bronsted acidity
of these catalyts also catalyses diene polymerization and favours retroalkylation of
alkylated anisole. The use of calcined clays strongly reduces these secondary reactions and higher chemical yields can be reached.
In a previous work [ 231 the results obtained on the alkylation of aromatics with
K10 montmorillonite exchanged with differents cations ( Ti4+, Fe + , Zr4+ , CL?+,
Zn+, Ce3+, Cr+, and Sn2+ ) were reported. The clays treated in air at 773 K

T. Cseri et al. /Applied Catalysis A: General 132 (1995) 141-155

143

showed practically pure Lewis acidity, while those dried at 393 K possessed
Bronsted acidity. The rate of alkylation was roughly related to Bronsted acidity
when the substrate was benzyl alcohol. In the case of benzyl chloride as alkylating
agent, the catalysts containing reducible cations ( Fe3+, Sn4+, Cu*+ ) exhibited
high activities in spite of their low number of Lewis acid sites. It was proposed that
an oxido-reduction was the first step of the reaction in that case.
It was interesting to investigate the series of clay based catalysts from Siid
Chemie. These K catalysts are industrial materials, possess high acidity, and are
frequently used as solid acids in organic catalysis. The aim of this work was to
characterize this series of acid treated clays, in order to investigate the source of
the activity of these solids in Friedel-Crafts alkylation. We report here the results
of characterization, and the catalytic properties for the alkylation of toluene by
benzyl alcohol and benzyl chloride.
2. Experimental
The K catalysts were purchased from Stid Chemie. Specific surface areas were
calculated by the BET equation, from nitrogen isotherms determined at 77 K
(Micromeritics ASAP 2000) on samples degassed at 523 K for 12 h before the
experiment. Chemical analyses were obtained by plasma emission spectroscopy.
Powder X-ray diffraction patterns were determined on a CGR Theta 60 instrument
using Cu Kc~l radiation.
2.1. Infrared spectroscopy
The self-supporting wafers (7 tons/cm2, 20 mg, 2 cm*) of clays were placed in
a quartz IR cell equipped with KBr windows and activated under vacuum (up to
1.2. 1O-4 Pa) at 393 K for 12 h. After cooling, the temperature was stabilised at
323 K and the cell was equilibrated with 260 Pa of pyridine (spectroscopic grade,
dried over Linde 4 A molecular sieve and further outgassed by the standard freezepump-thaw technique for 3 h) . The cell was then evacuated to 1.2. 10e4 Pa to
remove the gaseous and weakly adsorbed pyridine. The desorption was then continued at for 2 h at 393 K. After this treatment the infrared spectra were recorded,
at room temperature, with a FTIR Nicolet 320 spectrometer (resolution 2 cm- ) .
A quantitative determination of the two types of acidities was done by measuring
the area of the adsorption peaks. These values were related to the area of the structure
band of the clay in the same spectral region, the position of which does not change
on different samples. The band at 1545 cm- was considered as characteristic of
Bronsted acidity and the band at 1456-1448 cm- of Lewis acidity.
2.2. Solid state nuclear magnetic resonance (NMR) analyses
The MAS-NMR spectra were taken at 59.6 MHz forz9Si, and 104.2 MHz for
27A1, using a simple pulse-acquire-delay
sequence. The spectral widths used were

15 and 6.6 kHz, the pulse widths were 5.8 and 4.8 ps, and the relaxation delay 3 s
and 5 s for the *Si and 27A1 NMR, respectively. The shifts were referred to
Al ( N03) 3 aq for aluminium and tetramethylsilane for silicon. The silicon spectra
were done at a spinning frequency of 4-5 kHz, and the aluminium spectra were
performed with a spinning frequency of 14 kHz, in order to obtain a higher resolution. 25 000 to 50 000 scans were accumulated for *Si and 1100 to 10 000 scans
for 7A1, respectively.
2.3. Catalytic reactions
Two alkylating agents were investigated under standard conditions of reaction
[weight of catalyst: 100 mg, reaction mixture: toluene: 10 ml (94 mmol), alkylating
agent 6.25 mmol] , using a batch reactor at a temperature of 353 K.

7
CH2

CH3

C+b-RryllJ+Hx
Xz -Cl, -OH.

GC analyses were carried out in a Carlo Erba Fractovap 24 (HP 35900 AD

converter, Olivetti PC 286) equipped with flame ionization detector, PEG wetted
fused silica column (25 m, 0.32 mm, thickness of the stationary phase 1.2 pm),
helium as carrier gas, injector temperature of 548 K, detector temperature of 548
K and the following temperature program: 333 K (2 min)-6 K/min-423 K (30
min)--333 K.

3. Results
3.1. Characterization

of the structure of the solids

The X-ray diffraction patterns of the clays are reported in Fig. 1, and the chemical
analyses in Table 1. We can recall here that the base of K catalysts is the same
bavarian bentonite. This material appears as a rather pure montmorillonite, containing iron as is usually observed in natural materials.
From the indications of Stid Chemie [ 241, KSF is obtained from the original
material by treatment with sulfuric acid at room temperature. This treatment mainly
results in ion exchange of Na, Ca and Mg cations for protons, with only mild
extraction of Al, Mg and Fe from the structure. Consequently the montmorillonite
structure is retained. KlO, KPlO, KSFO and KS are activated with different mineral
acids at high temperature, and these treatments result in ion exchange, dealumina-

T. Cseri et al, /Applied

Cmd.wisA:

General 132 (1995) 141-155

BWU-isl
beotonite
KSF

KSF.0

KO
KlO

Fig.

I. Powder X-ray diffraction spectra of the K catalysts.

tion, and extraction of iron and magnesium. The montmorillonite structure is progressively destroyed, which results in a loss of crystallinity.
The surface areas of these materials are reported in Table 2. The Bavarian
bentonite and KSF show relatively low surface areas and no microporosity. Dealumination by a stronger acid treatment leads to the creation of large surface areas,
located mainly in mesopores, and the microporosity remains negligible.

Table I
Results of chemical analysis (weight-%)

of catalysts

Catalyst

Si%

AI%

Mg%

Fe%

St/AI + Mg

Hungarian bentonite (Mad)

Bavarian bentonite
K10
KO
KPlO
KS
KSF
KSFIO

31.87
25.4
3 I .54
3 I .59
3 I .62
32.14
23.69
27.65

10.29
IO.19
7.71
7.36
6.87
7.23
8.62
6.16

0.33
1.81
1.10
0.86
0.79
0.95
1.45
0.66

1.23
3.81
1.99
I .66
I .49
1.51
3.17
1.37

2.90
2.00
3.40
3.70
3.94
3.74
2.23
3.83

The Si and Al MAS NMR spectra of KlO have been reported previously
[ 251. These spectra relative to KPlO are reported in Fig. 2 and Fig. 3, as illustrations
of the general situation. They are similar to those of KlO. The chemical shifts
corresponding to the different Si and Al species observed for the different samples
are reported in Table 3 and Table 4. The original montmorillonites, and KSF show
only one type of silicon resonance, at - 90.9 ppm, close to the value reported for
Si in clays [26,27] , and an intense peak in the range 2-5 ppm characteristic of
octahedral Al, with small peaks at 55.5 and 67-70 ppm showing traces of tetrahedral
Al.
High temperature acid treatments induce the appearance of two other resonances,
at - 110 and - 101 ppm in the *Si spectra, and an increase of the intensity of the
peak at 70 ppm in the Al spectra. In their study of aluminosilicates, Magi et al.
[ 261 , assigned the signal at - 110 ppm to silicious impurities associated with the
clay, and a peak at - 93 ppm (close to our peak at - 9 1 ppm) to Si atoms in the
tetrahedral layer of the clay, linked to three other Si atoms and either to an Al or
Mg atom in the tetrahedral layer. The peak at - 100 ppm has been observed on 2/
1 clays calcined at high temperatures and is characteristic of the dehydroxylated
phases [ 281. This peak may be explained by the presence of Q4 ( 1Al) structural
Table 2
Results of the surface analysis of the catalysts
Catalyst

Specific
Surface area

Surface of
micropores(

Cm/&
Hungarian
bent&rite
Bavarian
bentonite
KIO
KO
KPIO
KS
KSF
KSFiO

ml/g )

Total pore
volume
(cmig)

Volume of
micropores

Average pore
size (A)

(cm/g)

31

5.1

0.040

0.0022

51

88

28.6

0.097

0.0122

44

229
268
169
322
9
117

2.5
6.8
9.8
2.8
0.7
19.9

0.320
0.380
0.300
0.465
0.01 I
0.215

0.0011
0.0290
0.0040
0.0009
0.000 1
0.0820

56
57
71
58
50
74

T. Cseri et al. /Applied Catalysis A: General 132 (1995) 141-155

147

units in three-dimensionally
connected aluminosilicate-like
structures formed by
SiOAl linkages between the silicate sheet and the gibbsite sheet during dehydroxylation. This interpretation, is supported by the observation of the2A1 NMR
signal at 65-74 ppm which is typical of tetrahedral Al in aluminosilicates.
3.2. Acidity of catalysts
The acidity of these solids can be investigated by many methods. A simple means
to evidence the acidity is to measure the pH of a suspension of clay in water: an
acid solid adsorbs OH- anions to neutralize the charge of protons, so the pH of the
water will reflect this increase of proton concentration in the solution. The results
are reported in Table 5. The original material is non-acidic and the solution remains
neutral, but the acid treatment creates acidity and the pH of the solution decreases.
This simple test permits to draw a scale of acidity in water, between the different
solids: KSFO > KSF > KPlO > KS > KlO > KO > Bavarian bentonite,
Hungarian bentonite.
Indeed it is doubful that this scale of acidity in water is valid in organic solvents
due to a different solvation of the acid sites. The adsorption of pyridine in the gas
phase, followed by infrared spectrometry is probably more representative in that
case. It also permits to establish the nature of the acid sites. The relative intensities
of the bands of pyridine adsorbed on Bronsted and Lewis sites are reported in

T. Cseri et al. /Applied

148

ollm

150

100

54

Catdyh

-50

A: Grnerul 132 (199.5) 141-155

-100

-150

-200

-250

-300

Fig. 3. Al MA.9 NMR spectrum of KPlO

Table 6, assuming that the vibrations at 1448-1455 cm- are associated to pyridine
coordinated to Lewis sites, and the vibration at 1545 cm- to pyridinium ions.
Small shifts are observed in the bands of pyridine adsorbed on Lewis sites, but the
magnitude of these shifts is not large enough to establish clear changes of the acid
strength between the different solids.
The intensities are normalized to the vibrations of the lattice in the spectral range
1920 cm- and 1800 cm- . The patterns of acidity obtained by this method are:
KS < KlO < KPlO < KSF < KSF/O, for Bronsted acidity and KPlO < KSF
< KSF/O < KS < KIO for Lewis acidity. Compared to the pattern obtained in
Table 3
Chemical shifts (ppm) of the different Si species observed on the K clays
Catalyst
Hungarian bentonite
Bavarian bentonite
K10
KO
KPIO
KS
KSF
KSFIO

- 90.6
-90.9
-90.7
- 90.5
-91.5
- 90.6
-90.2
-91.0

- 101.3
- 101.1
- 102.0
- 99.9

110.5
109.3
109.8
109.8

- 103.3

- 108.6

T. Cseri et al. /Applied Catalysis A: General 132 (1995) 141-155

149

Table 4
Chemical shifts (ppm) of the different Al species observed on the K clays
Catalyst

a, tetrahedral

a, tetrahedral

i17tetrahedral

?I, octahedral

Hungarian bentonite
Bavarian bentonite
KlO
KO
KPlO
KS
KSF
KSF/O

61.3
70.0
70.7
72.7
73.8
71.7
71.8
75.0

61.2

53.0
55.5

2.5
2.9
3.6
4.1
3.9
3.8
3.7

Table 5
pH of the suspension

of the K catalysts

56.8

(10% in water)

Catalyst

pH of 10% suspension

Hungarian bentonite
Bavarian bentonite
K 10
KO
KPlO
KS
KSF
KSF/O

7
7
4.5
5.5
1.8
3
1.5

1.3

Table 6
Relative intensities of the infrared bands of adsorbed pyridine on the clays dried at 393 K
Catalyst

Lewis acidity

Br#nsted acidity

KlO
KPlO
KS
KSF
KSF/O

1.91
0.42

2.23
2.32

1.02

1.76

0.59
0.61

2.35
3.09

water (Bavarian bentonite, Hungarian bentonite < KO < KlO < KS < KPlO <
KSF < KSFO), the acidity in water appears to be related to the Bronsted acidity
determined in the gas phase.
3.3. Catalytic alkylation of toluene
Two different alkylating agents were used: benzyl alcohol and benzyl chloride.
A complete conversion of the alkylating agent is observed within a few hours as
illustrated in Fig. 4 and Fig. 5.
The influence of the concentration of alkylating agent was determined on KlO
dried at 393 K. The variations of the initial rate of reaction as a function of the

150

T. Csrri CI al. /Applied

60

120

Catn/ysis

A: Gerwral

130

Reaction

240

132 (1995)

300

360

141-155

420

480

time (mid

Fig. 4. Changes of conversion as a function of time at 353 K, for the alkylation

the series of K catalysts dried at 393 K.

of toluene by benzyl chloride on

concentration are reported in Fig. 6: the reaction order changes from one at low
concentration to zero at high concentration. The observation of a zero order for
benzyl chloride suggests that this reactant is strongly adsorbed and saturates the
surface sites. Since the reaction is bimolecular, an Eley-Rideal mechanism can be
proposed. The observation of this zero order at higher concentrations suggests that
alkylation occurs by the reaction of adsorbed benzyl chloride with toluene from the
solution.
In the standard conditions used here, the concentration of 0.62 mol/l is in the
range where the zero order is observed, then the rate determined under these
conditions is a measure of the rate constant of the reaction. The catalytic activity
was then measured by the initial rate of raction which can be determined with good
precision.
The rates measured for the series of K catalysts are reported in Table 7. Since
the reactions are rather fast, the criterion of Weisz was used in orde to estimate
100

Z
80

60

40

Reaction

time (mid

Fig. 5. Changes of conversion as a function of time at 353 K, for the alkylation

the series of K catalysts dried at 393 K.

of toluene by benryl alcohol on

T. Cseri et al. /Applied

Catalysis A: General 132 (1995) 141-155

151

0.5

Concentration

1.5
01 benzyl

2
chloride

Fig. 6. Initial rate of alkylation as a function of the concentration

2.5
(mol/l)

of benzyl chloride on KlO dried at 393 K.

the influence of possible diffusional limitations. The criterion of Weisz [ 29 ] :

dN/dt.

~Ic~.R=/D,~-~ < 0.1

in which dN/dt (mol/g/s)

represents the rate of reaction, C, (mol/cm) the initial
substrate concentration, R (cm) the radius of the particles and Deff (cm*/s) the
effective diffusivity, predicts that the kinetics is controlled by the chemical process
when the rate is lower than 225 +lo- mol/g/h. In consequence, the rate of alkylation by benzyl chloride on KSF, measured at 7.50. 10e4 mol/g/h is underestimated, since it is limited by diffusion. The other rates are in the chemical regime.
The ortho-paru selectivity does not change greatly as a function of the conversion. The distribution of isomers at the end of the reaction is reported in Table 8:
only small changes are noticed when the catalyst is changed, and the larger influence
is that of the alkylating agent.
Influence of the temperature of treatment of the clays
The effect of this treatment was investigated in the case of KlO in order to
establish the influence of Lewis/Bronsted
acidity on the rates. The results are
reported in Table 9: the decrease of Bronsted acidity is clearly harmful to the
Table 7
Initial rates of reaction ( X 10 mol/g.h)
on acid treated clays dried at 393 K
Catalyst
Hungarian
KlO
KO
KPlO
KS
KSF
KSF/O

bentonite

for the alkylation

of toluene by benzyl alcohol and by benzyl chloride

Rate with benryl chloride

Rate with benayl alcohol

28
99
140
98
46
750
113

0
86
28
102
68
21
150

152

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132 1 IYY.7) IJI-155

Table 8
Ortho-para
selectivities for the alkylation of toluene by benzyl chloride ( BrCl) and benzyl alcohol
a reaction temperature of 353 K, on different clay catalysts treated under different conditions

Catalyst

Hungarian
KIO
KO
KPIO
KS
KSF
KSFIO

Temperature

bentonite

KlO
KIO
KIO
KIO
KIO

of treatment of catalyst (K)

BzOH) at

(7~)

Reagent

Isomer distribution

393
393
393
393
393
393
393

BzOH
BaOH
BrOH
BzOH
BzOH
BzOH
BzOH

44.3
44.8
44.0
45.2
41.6
46.8
46.0

55.1
55.2
56.0
54.8
58.4
53.2
54.0

393
413
513
673
713

BzCl
BzCl
BzCl
BzCl
BzCl

41.1

48.8
48.6
51.2
51.0

52.3
51.2
5 1.3
48.8
49.0

Table 9
Initial rates of alkylation of toluene with benzyl alcohol. Effect of the treatment temperature
( K)

Treatment temperature

Initial rate of reaction (

393
473
573
673
713

lo molig.

of a KIO catalyst

h)

8.60
2.55
I.41
0.91
0.36

60

120

180

240

Reaction

300
time

360

420

460

540

Imin)

Fig. 7. Comparison of the alkylations of toluene by benzyl chloride or benzyl alcohol. either alone or in a mixture
BzOH alone, (- + -) BzCl alone, (
*
.) BzOH competition, (
0.
) BzCI
(l/l).
( ---)
competition.

Catalysis A: General 132 (1995) 141-155

T. Cseri et al. /Applied

1.53

KSF
0
0

0,5

1.5

2.5

3.5

4.5

Intensity of PyH+ bands (au)

Fig. 8. Initial rates of alkylation

the different K catalysts.

of benzyl alcohol as a function of the intensity of pyridinium

bands measured for

activity when benzyl alcohol is used, which was expected for a proton catalyzed
reaction.
Finally, the competition between benzyl alcohol and benzyl chloride for the
alkylation of toluene was investigated on KlO dried at 393 K. The results reported
in Fig. 7 show that benzyl alcohol is alkylated first in the mixture, and following
that it is more strongly adsorbed that benzyl chloride. Benzyl chloride reacts when
all benzyl alcohol has been consumed, and the rate is lower than that observed for
the pure reactant. This must be due to the inhibiting effect of the water produced
by the reaction of benzyl alcohol.

4. Discussion
As reported before for KlO [ 281 , the K clays, excepted KSF which appears as
simply ion exchanged, have lost the structure classically assigned to montmorillonite. They appear as a complex mixture of the parent clay, silica and alumino-silicate
in which Al is tetrahedrally coordinated, which accounts for their high acidity.
It was previously observed [ 231, on KlO exchanged by different cations, that
the activity for benzyl alcohol alkylation was correlated to the number of protons,
but that no relationship existed between acidity and activity for the alkylation by
benzyl chloride. The present catalysts consist in a series of solids obtained from
the same parent clay, containing different amounts of iron, which is the only cation
of the solid which can be reduced at low temperature. Indeed in the present case
also, a reasonable correlation is observed between Bronsted acidity, measured by
the relative intensity of the infrared band relative to pyridinium ions, and activity
(Fig. 8). KSF falls out of the correlation, and appears to have a low activity
compared to its high acidity. It can be proposed that, since KSF retains the structure
of montmorillonite, it could be intercalated by pyridine, so some of the acid sites

i
0

0,5

1.5

Fe content

2.5

of catalyst

3,s

4,5

(%I

Fig. 9. Initial rates of alkylation of benryl chloride as a function of the iron content of the solid for the serie\ of K
catalysts.

measured by pyridine adsorption would not be accessible to the less polar reactants.
It clearly appears from these results that the activity for benzyl chloride alkylation
is practically independent of acidity: rather large changes of acidity result in similar
activities. A good correlation is, however, observed between the iron content of the
clay and catalytic activity for benzyl chloride alkylation (Fig. 9). This correlation
includes all the K catalysts and the Hungarian bentonite, which shows some activity
in this reaction, in spite of its lack of acidity. The effect of reducible cations
previously reported is then confirmed here by the influence of iron content of the
clay. This strongly suggests the possibility of a redox mechanism. There is, however, a large consensus on the fact that Friedel-Crafts reactions proceed through
carbocations [4] and it is also well known that radicals, which could be intermediates in redox processes, are powerful reductants, which should be readily oxidized
to carbocations in the presence of reducible metallic ions such as Fe+. The high
activity observed in the presence of iron could be reconciled with the classic ionic
mechanism of alkylation, assuming only a different initiation of the reaction, for
instance an homolytic rupture of the carbon-chlorine
bond followed by the oxidation of the radical:
Q-CHzCl+Fet

-+ a--CCHZ +Fe++Cl

Fe+ +Cl + Fe+ +Cl-

5. Conclusion
The influence of iron in heterogeneous catalysis is the counterpart of the known
activity of FeCl, for the same reaction in homogeneous phase. This high activity
of the iron component of the clays has been up to date rather underestimated and
should induce a reexamination of the literature in this field.

T. Cseri et al. /Applied

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155

Acknowledgements
T. Cseri thanks the Ministry of Education of France and the Foundation J6zsef
Varga of Technical University of Budapest for a grant. The financial help of the
E.C. (contract ERBCHRXCT930276)
is also aknowledged.

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