Applied Catalysis A: General 218 (2001) 25–30

Comparison of different Lewis acid supported on hydroxyapatite

as new catalysts of Friedel–Crafts alkylation
Saı̈d Sebti∗ , Rachid Tahir, Rachid Nazih, Saı̈d Boulaajaj
Laboratoire de Chimie Organique Appliquée et Catalyse, Faculté des Sciences, Ben M’Sik,
Université Hassan II, B.P. 7955, Casablanca, Morocco
Received 9 January 2001; received in revised form 13 March 2001; accepted 15 March 2001

Abstract
ZnCl2 , NiCl2 and CuCl2 supported on hydroxyapatite (HAP), as a new solid support, catalyse the Friedel–Crafts alkylation
of benzene, toluene and p-xylene by benzyl chloride. The reaction proceeds selectively to monoalkyl-compounds and in a
short reaction time. The best catalytic activities were observed with the zinc catalysts. © 2001 Elsevier Science B.V. All rights
reserved.
Keywords: Hydroxyapatite; Friedel–Crafts alkylation; Heterogeneous catalysis; Metal halides

1. Introduction hydration of nitriles [13] and Friedel–Crafts alky-

Alternative ways to replace the common Lewis
acids, such as AlCl3 by catalytic reagents in Friedel–
Crafts reactions are of considerable industrial inter-
est because these stoichiometric reagents, which are
destroyed after usual aqueous workup required to iso-
late the organic products, cause severe environmental
pollution.
Therefore, in recent years, a great deal of effort has
been directed towards the promotion of this reaction
and several synthetic procedures have been reported
for the Friedel–Crafts reaction. These methods involve
montmorillonite [1,2], zeolites [3,4], sol–gel-derived
silica or aluminosilicates [5–7] and other catalysts
[8–11].
Within our own work, many reactions in hetero-
geneous media, such as Knoevenagel reactions [12],
∗ Corresponding author. Tel.: +212-61464819;
fax: +212-22704675.
E-mail address: lcoacasa@hotmail.com (S. Sebti).
lation [14] have been devised earlier using natural
phosphates and natural phosphates doped with min-
eral salts.
Recently, we have synthesised an apatitic structure
as a new family of phosphates catalysts. Thus, we
have demonstrated that fluorapatite [15] is a very good
catalyst of the Knoevenagel condensation.
In this paper, we describe the use of the hydroxyap-
atite (HAP) as a new solid support, alone or activated
with metal halides, such as ZnCl2 , NiCl2 and CuCl2 ,
in the Friedel–Crafts alkylation (Scheme 1). Indeed,
HAP has recently received much attention [16,17] in
view of its potential usefulness as an adsorbent and
most importantly as a catalyst in solid–gas reactions
[18,19].
2. Experimental
The 1 H NMR experiments were carried out on a
Varian VXR-Unity 300 (300 MHz). Surface area and

0926-860X/01/$ – see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 6 - 8 6 0 X ( 0 1 ) 0 0 5 9 9 - 3
26 S. Sebti et al. / Applied Catalysis A: General 218 (2001) 25–30

Scheme 1.

pore volume determinations were carried out at 77 K

using a Coulter SA3100 instrument with an automated
gas volumetric method employing nitrogen as adsor-
bate. Gas chromatographic (GC) was carried out using
a Shimadzu GC-14B gas chromatograph. Analysis was
carried out with the aid of packed column containing
3% OV-17 On, CWHP. Products were identified by
GC–MS using a Hewlett Packard 5890 II GC (methyl
silicon column 25 m × 0.2 mm × 0.33 ␮m) interfaced
to VG-Autospec mass spectrometer. Infrared spectra
were performed on a FTIR (ATI Mattson–Genesis
Series). The nature and purity of the synthesized HAP
was checked by X-ray powder diffraction (Philips
1710 diffractometer).
2.1. Preparation and characterisation of catalysts
The synthesis of HAP was carried out by the
co-precipitation method [20,21] (Scheme 2). 250 ml
of a solution containing 7.92 g of diammonium hy-
drogen phosphate (Riedel-de Haën, 99%), maintained
at a pH greater than 12, by addition of ammonium
hydroxide (BDH) (60–70 ml), were dropped under
constant stirring into 150 ml of a solution containing
Scheme 2.
23.6 g of calcium nitrate [Ca(NO3 )2 ·4H2 O] (Riedel-de
Haën, 98%). The suspension was refluxed for 4 h.
Doubly distilled water (DDW) was used to prepare the
solutions. The HAP crystallites were filtered, washed
with DDW, dried overnight at 80◦ C and calcined in
air at 700◦ C for 30 min before use.
The structure of obtained apatite was confirmed by
X-ray diffraction, infrared spectra and chemical anal-
ysis. The hydroxyapatite crystallizes in the hexagonal
system with the space group P63/m . The lattice param-
eters of the prepared HAP are in excellent agreement
with standard data: a = 6.883 Å and c = 9.422 Å. The
surface area of calcined HAP was determined by the
BET method from the adsorption–desorption isotherm

Table 1
Benzylation of benzene, toluene and p-xylene over hydroxyapatite
Substrate Catalyst (g) Time Conversiona (isolated Monoalkyl compoundc Dialkyl compoundc (%)
product)b (%) (ortho/para)d (%)
Benzene 1 48 h (76) 70 30
0.1 48 h (50) 68 32
Toluene 1 120 min 95 (93) 87 (37/63) 13
0.1 12 h (94) 88 (39/61) 12
p-Xylene 1 90 min 99 (94) 87 13
0.1 6h (94) 87 13
a Conversion of benzyl chloride determined by GC-mass.
b Yield of isolated products after distillation.
c Percentage of isolated products after distillation.
d Composition determined by 1 H NMR.
 S. Sebti et al. / Applied Catalysis A: General 218 (2001) 25–30 27

of nitrogen at its liquid temperature (77 K) and was
found to be S = 38.26 m2 g−1 . The total pore volume
was calculated by the BJH method at P /P0 = 0.98
(VT = 0.157 cm3 g−1 ).
The preparation of MCl2 /HAP (M = Zn, Ni or Cu)
was as follows: 10 mmol of MCl2 (Riedel-de Haën,
97–98%) and 10 g of HAP were mixed in 100 ml of
water and then evaporated to dryness and dried for 2 h
at 150◦ C before use.
2.2. Reaction procedure
The solution of benzyl chloride (Fluka, 99%)
(9 mmol) in benzene (BDH, 99%), toluene (BDH,
99%) or p-xylene (Janssen, 99%) (10 ml) was refluxed
in the presence of HAP, ZnCl2 /HAP, CuCl2 /HAP or
NiCl2 /HAP (1 or 0.1 g). The mixture was stirred. The
reaction was monitored by GC. All obtained prod-
ucts were purified by distillation under vacuum and

Table 2
Benzylation of benzene, toluene and p-xylene with different prepared catalysts
Substrate Catalyst Catalyst Time Conversiona (isolated Monoalkyl compoundc Dialkyl
(g) product)b (%) (ortho/para)d (%) compoundc (%)
Benzene HAP 1 48 h (76) 70 30
0.1 48 h (50) 68 32
ZnCl2 /HAP 1 15 min 98 (93) 78 22
0.1 120 min 87 (85) 78 22
0.1 150 min 99 (93) 83 17
NiCl2 /HAP 1 2h (96) 71 29
0.1 12 h (93) 80 22
CuCl2 /HAP 1 3h (94) 79 21
0.1 24 h (51) 78 22
Toluene HAP 1 120 min 95 (93) 87 (37/63) 13
0.1 12 h (94) 88 (39/61) 12
ZnCl2 /HAP 1 2 min 97 (94) 91 (36/64) 9
0.1 10 min 99 (96) 89 (36/64) 11
NiCl2 /HAP 1 10 min 99 (95) 95 (36/64) 5
0.1 180 min 99 (96) 94 (37/63) 6
CuCl2 /HAP 1 30 min (98) 87 (35/65) 13
0.1 180 min 96 (95) 89 (36/64) 11
p-Xylene HAP 1 90 min 99 (94) 87 13
0.1 90 min (49) 90 10
0.1 6h (94) 87 13
ZnCl2 /HAP 1 2 min 99 (96) 93 7
0.1 2 min 67
0.1 5 min 99 (93) 89 11
NiCl2 /HAP 1 5 min 95 (91) 89 11
0.1 5 min 42
0.1 30 min 99 (92) 90 10
CuCl2 /HAP 1 7 min 99 (94) 91 9
0.1 30 min 94 (88) 90 10
a Conversion of benzyl chloride determined by GC-mass.
b Yield of isolated products after distillation.
c Percentage of isolated products after distillation.
d Composition determined by 1 H NMR.
28 S. Sebti et al. / Applied Catalysis A: General 218 (2001) 25–30
Fig. 1. Benzylation of benzene, toluene and p-xylene in presence
of HAP (0.1 g).
identified by 1 H NMR and IR spectroscopy. The
results obtained are in Tables 1 and 2.
3. Results and discussion
3.1. Benzylation of benzene, toluene and p-xylene
over hydroxyapatite
We have carried out the Friedel–Crafts alkylation in
presence of hydroxyapatite alone. The results obtained
in the benzylation of benzene, toluene and p-xylene
with 0.1 g of catalyst are shown in Fig. 1. The yields
Fig. 2. Benzene benzylation with CuCl2 /HAP, NiCl2 /HAP, and ZnCl2 /HAP.
exceed 90% for toluene and p-xylene. The best yield
obtained for benzylation of benzene is 50% in 48 h.
It is noteworthy that the reactivity of the aromatic
nucleus increases with the number of electron donor
groups. So, p-xylene with two methyl groups reacts
more easily than the toluene with only one group and
much more than benzene. These results show that the
HAP is an interesting new catalyst which can easily
promote the Friedel–Crafts alkylation.
The best results obtained in the Friedel–Crafts
benzylation in the presence of HAP are in Table 1.
In all cases, the reaction proceeds selectively to
monoalkyl-compounds. Thus, products of monoalky-
lation are obtained mostly: benzene benzylation (68%
monoalkyl, 32% dialkyl); toluene benzylation (88%
monoalkyl, 12% dialkyl); p-xylene benzylation (87%
monoalkyl, 13% dialkyl). The increase of the mass of
the support from 0.1 g to 1 g permits a considerable
increase of the reaction rate.
The results described in Fig. 1 and Table 1, show
that HAP is an acidic catalyst which can contribute
to the development of cleaner catalytic processes and
is able to promote the Friedel–Crafts benzylation and
is also easy to prepare as detailed above.
3.2. Activation of HAP with metal halides
First, we compared the catalytic activity of ZnCl2 ,
NiCl2 and CuCl2 supported on hydroxyapatite in the
reaction of benzene (Fig. 2), toluene (Fig. 3) and
 S. Sebti et al. / Applied Catalysis A: General 218 (2001) 25–30 29

Fig. 3. Toluene benzylation with CuCl2 /HAP, NiCl2 /HAP, and ZnCl2 /HAP.

p-xylene (Fig. 4) with benzyl chloride in the presence
of the prepared MCl2 /HAP (0.1 g).
For all cases, the best catalytic activity was observed
with the zinc containing catalyst. So, the activity
of ZnCl2 /HAP is considerably higher than those of
NiCl2 /HAP and CuCl2 /HAP. In the benzene benzyla-
tion, CuCl2 supported on hydroxyapatite is the least
active. In this case, only 51% of benzyl chloride con-
version is obtained in 24 h. However, in the toluene
and p-xylene benzylation, the difference between
CuCl2 /HAP and NiCl2 /HAP is not significant.
The best results obtained in the Friedel–Crafts ben-
zylation in the presence of HAP alone and doped are
in Table 2.
ZnCl2 /HAP, NiCl2 /HAP and CuCl2 /HAP promote
the reaction much better than hydroxyapatite alone.
High selectivity toward monoalkyl-compounds was
obtained with all catalysts. Thus, the selectivity to-
wards monoalkylation is greater in the case of toluene
and p-xylene with a ratio monoalkyl/dialkyl which
varies between 95/5 and 87/13, whereas in the case
of benzene this proportion varies between 83/17 and

Fig. 4. p-Xylene benzylation with CuCl2 /HAP, NiCl2 /HAP, and ZnCl2 /HAP.
30 S. Sebti et al. / Applied Catalysis A: General 218 (2001) 25–30
68/32. Also, for the alkylation of toluene, we note the
predominance of para-substituted compound (about
63% para/37% ortho).
Finally, for all doped catalysts, the reactivity of the
aromatic nucleus increases with the number of electron
donor groups as well as the HAP alone.
Otherwise, we have carried out the toluene benzy-
lation in the presence of MCl2 alone using the same
quantity contained in 0.1 g of MCl2 /HAP. The results
obtained with ZnCl2 , NiCl2 and CuCl2 are 17%
(10 min), 8% (180 min) and 6% (180 min), respec-
tively. The impregnation of MCl2 on HAP provokes
a considerable synergistic effect (Table 2).
We believe that these new supported reagents
represent an important breakthrough in the devel-
opment of solid catalysts. The high reactivity and
specificity of our catalysts coupled with their ease
of use and reduced environmental problems makes
them attractive alternatives to homogeneous acidic
reagents.
Acknowledgements
Financial assistance of the ministry of educa-
tion, government of Morocco (PROTARS, P2T3/59)
is gratefully acknowledged. We also thank the
“Office Chérifien des Phosphates (OCP)” and “Cen-
tre d’Etudes et de Recherches sur les Phosphates
Minéraux (CERPHOS)” for their support. Thanks
are expressed to Prof. J. A. Mayoral, Universidad de
Zaragoza, for cooperation in some of work presented
here.
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