Applied Catalysis A: General 197 (2000) 213219

FriedelCrafts acylation of toluene catalyzed by solid superacids

Kazushi Arata , Hideo Nakamura, Miyuki Shouji
Department of Science, Hokkaido University of Education, Hachiman-cho, Hakodate 040-8567, Japan
Received 17 May 1999; received in revised form 24 September 1999; accepted 4 October 1999

Abstract
Benzoylation of toluene (141 mmol) with 2 mmol of benzoic anhydride or benzoyl chloride was carried out in liq-
uid phase over 0.5 g of solid superacids of sulfated and supported metal oxides at 100 C for 3 h. Yields of o-, m-, and
p-methylbenzophenones in the distribution of 2030% o-, 24% m-, and 7080% p-isomers were 92, 48, 28, 27, 26, and 0%
for the sulfated oxides of SO4 /ZrO2 , SO4 /SnO2 , SO4 /TiO2 , SO4 /Al2 O3 , SO4 /HfO2 , and SO4 /Fe2 O3 with benzoic anhydride as
the acylating reagent. The supported oxides of WO3 /ZrO2 , WO3 /TiO2 , WO3 /SnO2 , and MoO3 /ZrO2 gave yields of 55, 26, 16,
and 15%, respectively; WO3 /Fe2 O3 and B2 O3 /ZrO2 gave no yields. As a whole, yields by the reactions with benzoyl chloride
were lower than those with the anhydride. When benzoyl chloride was the acylating agent, the reactions over SO4 /Fe2 O3 and
WO3 /Fe2 O3 were homogeneously catalyzed by FeCl3 produced during the reaction, though other reactions were heteroge-
neously catalytic. The activity of SO4 /ZrO2 was largely promoted by the addition of Pt and Ru (2 wt.%). Silicaaluminas,
zeolites, and mordenites were almost inactive under the conditions. It was shown from the acid strength and the catalytic
activity for disproportionation of toluene that inactivity of the aluminosilicates for the acylation is based on their catalytic
action by Brnsted acid sites. A rough relationship was obtained between the highest acid strength of the present catalysts and
the acylated yields. The present catalysts were also satisfactorily effective for the acetylation of toluene with acetic anhydride
and acetyl chloride. 2000 Elsevier Science B.V. All rights reserved.
Keywords: Acylation; Benzoylation; Acetylation; Solid superacids; Sulfated metal oxides; Supported metal oxides; Zeolites

1. Introduction Therefore, there is much interest in ways to catalyze

The FriedelCrafts reaction (alkylation and acy-
lation of aromatic compounds) has been studied
extensively in the past using various Lewis acid cat-
alysts (BF3 , AlCl3 , FeCl3 , TiCl4 ) and protonic acids
(HF, H2 SO4 ) [13]. The acylation reactions require
molar amounts of the Lewis catalyst, which form
complexes with both the acylating reagent and the
carbonyl product; thus, work up is needed to decom-
pose the complexes, and the catalyst is not reusable.
Corresponding author. Tel.: +81-138444286;
fax: +81-138444286.
E-mail address: karata@cc.hokkyodai.ac.jp (K. Arata)
these reactions with solid acids which do not form
such complexes with carbonyl compounds. However,
a high acidic strength is required on the surface to
catalyze the acylation; a superacid, with acid strength
stronger than that of 100% H2 SO4 , is desired.
Over a wide range of solid acids zeolites and
silicaaluminas hold high acidities on their surface
and have received much attention in the petroleum
industry and in organic syntheses. However, little at-
tention has been given to those silicoaluminic acids
as catalysts for the FriedelCrafts acylation. Chiche
and others reported the acylation of toluene and
p-xylene by various carboxylic acids catalyzed by a
Y-faujasite-type zeolite exchanged with Ce3+ cation,

0926-860X/00/$ see front matter 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 6 - 8 6 0 X ( 9 9 ) 0 0 4 8 4 - 6
214 K. Arata et al. / Applied Catalysis A: General 197 (2000) 213219
but the conditions were quite severe: operating in an
autoclave heated at 150 C for 2 days [4]. Olah and
co-workers investigated the heterogeneous catalysis
by a perfluorinated resinsulfonic acid (Nafion-H) for
the acylation of substituted benzenes [5]. The reac-
tions were conducted by heating a stirred mixture
of acid chloride, aromatics, and the solid Nafion-H
catalyst under reflux. Satisfactory results were ob-
tained, though the catalyst was not a usual solid acid
consisting of metal oxides.
Solid superacids, sulfated zirconia and alumina
(SO4 /ZrO2 and SO4 /Al2 O3 ) showed activities for
the benzoylation of toluene with benzoyl chloride
and benzoic anhydride at temperatures below reflux
of the mixture [6,7]. Tungsten oxide supported on
zirconia (WO3 /ZrO2 ), a superacid by the system of
metal oxides, was also active for the acylation [8].
We have reported that, on the oxide surfaces of Fe,
Ti, Hf, Sn, and Si, superacids with an acidity stronger
than that of 100% H2 SO4 are generated by addition
of the sulfate species [9]. Superacids by metal oxides
were also synthesized in the same manner as those of
the sulfate superacids by supporting SnO2 , TiO2 , and
Fe2 O3 with WO3 and ZrO2 with MoO3 and B2 O3
[10]. Metal-promoted superacids, which were highly
active for the reaction of butane to isobutane, were
prepared recently: PtSO4 /ZrO2 , RuSO4 /ZrO2 , and
Fe2 O3 /ZrO2 [1113].
Most of the above-mentioned superacids have not
been examined as to the acylation. The present pa-
per is concerned with a comparative study of those
superacids in company with several zeolites and
silicaaluminas for the benzoylation of toluene with
benzoic anhydride and benzoyl chloride at mild tem-
peratures below reflux operating in a batch mode.
Several catalysts were also examined in a less reac-
tive acylation: the acetylation of toluene with acetic
anhydride or acetyl chloride.
2. Experimental
2.1. Catalyst preparation
2.1.1. Preparation of metal hydroxides
1. Zr(OH)4 : the hydroxide was obtained by hydrolyz-
ing ZrOCl2 with aqueous ammonia to pH 8 at a
temperature of 6070 C; aqueous ammonia so-
lution (28%) was added dropwise with stirring
into 100 g of ZrOCl2 8H2 O dissolved in 2 l of
distilled hot water; then, the precipitated solution
was kept at 6070 C for 3 h; the precipitate was
washed several times with hot water, and finally
dried.
2. Sn(OH)4 : aqueous ammonia was added into a so-
lution of SnCl4 xH2 O (10 g) in water (2 l) with
stirring at 60 C, the final pH of the solution be-
ing 8. The precipitates were washed by decanta-
tion five times, using 1 l of hot water for each, and
dried.
3. H4 TiO4 : a 290 ml volume of Ti[OCH(CH3 )2 ]4
was added to 2 l of distilled water in a 5 l beaker
with stirring; the white precipitates which formed
were dissolved by adding 250 cm3 of conc. HNO3 .
Ammonium hydroxide was added into the aque-
ous solution with stirring until the pH of the
solution reached 8, followed by washing the pre-
cipitates by decantation of the 5 l beaker twice and
drying.
4. Hf(OH)4 : the hydroxide was obtained by hydolyz-
ing HfCl4 with ammonia water to pH 8, washing
the precipitates, and drying.
5. Fe(OH)3 : to a solution of Fe(NO3 )3 9H2 O (500 g)
dissolved in 2 l of water in a 5 l beaker was added
aqueous ammonia with stirring to precipitate
Fe(OH)3 . The aqueous portion was decanted from
the precipitate after allowing the solution to stand.
Then, the precipitates were washed by decantation
seven to eight times, and dried.
All of the precipitated hydrogels were dried at
100 C for 24 h and powdered to below 100 mesh.
2.1.2. Sulfate treatment of metal hydroxides
Materials prepared as above were treated with sul-
fate ions by exposing 2 g of dried and powdered metal
hydroxide in 30 ml of aqueous sulfuric acid on a glass
filter for 1 h, followed by filtering, drying in a desic-
cator at room temperature, and finally calcining. The
concentration of H2 SO4 was 1 N for the hydoxides of
Ti and Zr, 0.5 N for Fe, 2 N for Hf, and 6 N for Sn;
the calcination temperature was 500 C for Fe, 525 C
for Ti, 550 C for Sn, 600 C for Zr, and 700 C for Hf.
The catalysts prepared are indicated as SO4 /ZrO2 ,
SO4 /Fe2 O3 , SO4 /TiO2 , SO4 /HfO2 , and SO4 /SnO2 .
 K. Arata et al. / Applied Catalysis A: General 197 (2000) 213219
SO4 /Al2 O3 was prepared by powdering -Al2 O3
(Japan Chromato, AE-11), followed by treating with
5 N H2 SO4 and calcining at 650 C.
Two more SO4 /ZrO2 catalysts were prepared. One
was prepared by calcining sulfated zirconia of Wako
Pure Chemical Industries at 550 C. The other was
prepared by powdering zirconium hydroxide, XZO
632/03, of MEL Chemicals (dried at 100 C for 24 h),
followed by treating with 1 N H2 SO4 and calcin-
ing at 600 C. The former catalyst was denoted as
SO4 /ZrO2 -1 and the latter as SO4 /ZrO2 -3; thus, the
sulfated zirconia prepared from ZrOCl2 was denoted
as SO4 /ZrO2 -2.
All the catalysts were calcined in Pyrex glass tubes
in air for 3 h and sealed in ampoules while hot, to
avoid humidity until use.
2.1.3. Preparation of Pt- and Ru-added sulfated
zirconias
PtSO4 /ZrO2 -3 was obtained by treating Zr(OH)4
(XZO 632/03 MEL Chemicals) with 1 N H2 SO4 ,
followed by drying, impregnating with aqueous
H2 PtCl6 6H2 O (to obtain 2 wt.% Pt in the final cat-
alyst after calcination), evaporating residual water,
drying, and calcining in air at 600 C for 3 h.
RuSO4 /ZrO2 -3 was obtained by impregnating
Zr(OH)4 (XZO 632/03) with an aqueous solution of
RuCl3 nH2 O, followed by evaporating residual water,
drying at 300 C for 3 h, treating with 1 N H2 SO4 ,
drying, and finally calcining in air at 550 C for 3 h,
the concentration being 2 wt.% Ru based on the
hydroxide.
2.1.4. Preparation of superacids by metal oxides
The catalysts of WO3 /ZrO2 -3, WO3 /TiO2 , WO3 /
SnO2 , WO3 /Fe2 O3 , and MoO3 /ZrO2 -3 were ob-
tained by drying the hydroxides of Zr, Ti, Sn,
and Fe (prepared in Section 2.1.1) at 300 C, fol-
lowed by impregnating with aqueous ammonium
metatungstate (NH4 )6 (H2 W12 O40 ) or ammonium
molybdate (NH4 )6 Mo7 O24 4H2 O), evaporating water
at room temperature, drying, and calcining in air. The
concentration was 15 wt.% W or 5 wt.% Mo metal
based on the hydroxides. The calcination temperature
was 700 C for WO3 /TiO2 and WO3 /Fe2 O3 , 800 C
for WO3 /ZrO2 -3 and MoO3 /ZrO2 -3, and 1000 C for
WO3 /SnO2 .
215
B2 O3 /ZrO2 -3 was prepared by impregnating
Zr(OH)4 (XZO 632/03) with aqueous boric acid
(H3 BO3 ), followed by evaporating water and calcin-
ing in air at 550 C for 3 h (5 wt.% B).
Fe2 O3 /ZrO2 -3 was obtained by impregnating
Zr(OH)4 (XZO 632/03) with an aqueous solution of
Fe(NO3 )3 , followed by evaporating residual water,
drying at 300 C for 3 h, treating with 1 N H2 SO4 , dry-
ing, and calcining in air at 700 C for 26 h (2 wt.% Fe).
The calcination temperature of the present materials
is high, above the melting point of Pyrex glass. Thus,
the calcination at temperatures above 700 C was per-
formed in a ceramic crucible, followed by calcining
in Pyrex glass tubes at 500 C for 1 h and sealing in
ampoules until use.
2.1.5. Preparation of aluminosilicates
Silicaaluminas and acidic zeolites and mordenites
were supplied from the Catalysis Society of Japan
as reference catalysts and calcined at 500 C for 3 h:
JRC-SAH-1 and JRC-SAL-2 with SiO2 /Al2 O3 ratios
of 2.5 and 6 for silicaaluminas; JRC-Z5-70H and
JRC-Z-HY5.6 with the ratios of 70 and 5.6 for zeo-
lites: JRC-Z-HM20 and JRC-Z-HM15 with the ratios
of 20 and 15 for mordenites; respectively. These were
denoted as SiO2 Al2 O3 -1 and -2, zeolite-1 and -2, and
mordenite-1 and -2, respectively.
2.2. Reaction procedure
2.2.1. Acylation of toluene
The acylation was carried out with a mixture of
15 ml (141 mmol) of toluene, 2 mmol of acylating
reagent (0.281 g for benzoyl chloride, 0.452 g for ben-
zoic anhydride, 0.157 g for acetyl chloride, 0.204 g
for acetic anhydride), 0.5 g of catalyst, and 0.185 g
(1 mmol) of tridecane as an internal standard with
stirring under nitrogen atmosphere. A small amount
of the sample was withdrawn periodically with a 1 ml
syringe, diluted with ethyl acetate, separated from
the catalyst by filtration, and analyzed by gasliquid
chromatography with an FID detector using a 25 m
column of OV-1701 BONDED (180 C for benzoyla-
tion, 150180 C for acetylation). The product isomers
were identified by the spectral comparison with au-
thentic samples. Since toluene was in excess, yields
were based on the acylating reagents.
216 K. Arata et al. / Applied Catalysis A: General 197 (2000) 213219

2.2.2. Disproportionation of toluene the homogeneous FriedelCrafts acylation, the reac-

Disproportionation of toluene was carried out in a tion is generally performed with an acid chloride as the
microcatalytic pulse reactor with a fixed-bed catalyst acylating agent and with metal halides such as FeCl3
(He carrier gas 20 ml/min, catalyst 0.05 g, pulse size or AlCl3 as catalysts. In the reactions with SO4 /Fe2 O3
1 l); effluent products were directly introduced into and WO3 /Fe2 O3 , a question arises whether the ac-
a g.c. column for analysis (SE-30, 2 m, 90 C). The tive species are on the solid surface or in the liq-
catalyst was again heated at 300 C for 1 h in the He uid as FeCl3 derived from the reaction of Fe2 O3 and
flow before reaction. Activities were compared with HCl produced or Cl , caused by the formation of the
the first pulse value. acyl cation (PhCO+ ) from benzoyl chloride. When
the catalysts were removed from the reaction mix-
ture by filtration, the mixture was found to be col-
3. Results and discussion ored brown. This color was brought about by Fe3+ ,
though the mixture over most of the catalysts was
The benzoylation of toluene with benzoic anhy- clear. In fact, Cl was detected in the mixture, and the
dride or benzoyl chloride, a typical example of the mixture turned clear when washed with water. That
FriedelCrafts acylations, was carried out in liquid the reaction over SO4 /Fe2 O3 and WO3 /Fe2 O3 is ho-
phase over various solid superacids of sulfated and mogeneous can be obvious from the results that the
supported metal oxides along with silicoaluminic SO4 /Fe2 O3 and WO3 /Fe2 O3 catalysts were not active
acids at 100 C; the results for 3 h are shown in when the reaction was performed with benzoic anhy-
Table 1 for sulfated metal oxides and in Table 2 for dride, though the yields were 38 and 74% in the reac-
supported metal oxides, silicaaluminas, zeolites, and tion with benzoyl chloride. The inactivity with the an-
mordenites. hydride is based on their weak acidity on the surface,
Most of the reactions showed a continual increase as will be described later. The reaction mixture over
of yield with time, and were thus judged to be hetero- MoO3 /ZrO2 with benzoyl chloride was also slightly
geneously catalytic, but the materials of SO4 /Fe2 O3 bluish, but the reaction progressed continuously.
and WO3 /Fe2 O3 failed to react further after 3060 min The reactivity with acylating reagents is generally
when benzoyl chloride was the acylating reagent. In PhCOCl > (PhCO)2 O > PhCO2 H; strong acid sites are
needed for the formation of acyl cation (PhCO+ ) from
Table 1 the anhydride. However, the present results are not
Benzoylation of toluene with benzoic anhydride or benzoyl chlo- coincident with the reactivity, in particular, with the
ride over sulfated metal oxides at 100 C for 3 h case of SO4 /ZrO2 -1. A supplementary examination
Catalyst Benzoic anhydride Beyzoyl chloride with the SO4 /ZrO2 -1 catalyst gave the same results as
Yield Isomers Yield Isomers those in Table 1. The reason is not clear at the present
(%) (%) (%) (%) stage: probably, strong interaction between oxygens
o- m- p- o- m- p-
of the anhydride and acid sites on the surface; this
should be a strong point of the present catalysts for the
SO4 /ZrO2 -1 92 27 0 73 22 31 0 69 acylation. Benzoylation by the benzoic acid produced
SO4 /ZrO2 -2 52 30 2 68 60 30 2 68
SO4 /SnO2 48 25 4 72 52 24 3 73
was not caused under the conditions when the reaction
SO4 /TiO2 28 23 4 73 17 24 3 73 was performed with (PhCO)2 O; the reaction occurred
SO4 /Al2 O3 27 24 4 72 18 23 4 74 at temperatures above reflux of the mixture [6].
SO4 /HfO2 26 25 3 72 Among the solid superacids synthesized so far, the
SO4 /Fe2 O3 0 38 27 0 73 SO4 /ZrO2 catalyst showed the highest acid strength
SO4 /ZrO2 -3 25 30 0 70
PtSO4 /ZrO2 -3 79 28 3 69
(Ho < 16) [10] and gave the highest yield in the
RuSO4 /ZrO2 -3 40 25 2 73 benzoylation as shown in Tables 13. Table 1, how-
SO4 /ZrO2 -3a 19 26 2 71 ever, shows how the preparation method controls the
PtSO4 /ZrO2 -3a 71 28 2 70 catalytic activity; SO4 /ZrO2 -1 is especially the most
RuSO4 /ZrO2 -3a 35 25 2 73 effective when carried out with the anhydride, in com-
a Reaction at 90 C. parison with SO4 /ZrO2 -2 and -3. The SO4 /ZrO2 -1
 K. Arata et al. / Applied Catalysis A: General 197 (2000) 213219 217

Table 2
Benzoylation of toluene with benzoic anhydride or benzoyl chloride over supported metal oxides and silicoaluminic acids at 100 C for 3 h
Catalyst Benzoic anhydride Beyzoyl chloride

Yield (%) Isomers (%) Yield (%) Isomers (%)

o- m- p- o- m- p-
WO3 /ZrO2 -3 55 31 0 69 19 31 0 69
WO3 /TiO2 26 19 3 78 20 31 0 69
WO3 /SnO2 16 18 0 82 14 18 0 82
WO3 /Fe2 O3 0 74 16 0 82
MoO3 /ZrO2 -3 15 23 2 75 18 23 3 74
B2 O3 /ZrO2 -3 0
Fe2 O3 /ZrO2 -3 49 26 1 73
SiO2 A12 O3 -1 0 0
SiO2 A12 O3 -2 0 0
Zeolite-1 0 0
Zeolite-2 0 0
Mordenite-1 1 0 0 100 1 0 0 100
Mordenite-2 2 12 0 88 3 10 0 90

Table 3
Acetylation of toluene with acetic anhydride at 100 C for 3 h
Catalyst Yield (%) Isomers (%)
o- m- p-
SO4 /ZrO2 -1 7 2 0 98
PtSO4 /ZrO2 -3 7 2 0 98
WO3 /ZrO2 -3 3 2 0 98
matter is exceptionally prepared as a catalyst suitable
for the organic synthesis 1 .
It is reported that impregnation of SO4 /ZrO2 with
Fe and Mn as well as with noble metals such as Pt and
Ru leads to pronounced activity for the reaction of bu-
tane to isobutane [10]; in particular, impregnation with
a large quantity of Pt and Ru is exceedingly effective
[11,12]. Thus, SO4 /ZrO2 -3 was modified by the addi-
tion of Pt and Ru (2 wt.%) and examined in the benzoy-
lation with the anhydride. The activities were largely
promoted by the addition of the metals, as shown in
Table 1. A supplementary examination was tried at the
lower temperature, 90 C; the enhancement by the ad-
dition of Pt and Ru was 3.5 and two times, respectively.
It was assumed from the case of butane that the ac-
tivity enhancement would be uncertain because it was
reported that the promotion by the addition of metals
was not based on acidity but on the metallic effect for
1 A private communication from the company.
the dehydrogenation of butane to butene, followed by
dimerization and cracking to isobutane [14,15]. Acid-
ity of metal-promoted sulfated zirconias is not char-
acterized in detail, and such study is desired. As per
this point of view, Fe2 O3 /ZrO2 -3 prepared in the same
manner as RuSO4 /ZrO2 -3 is also a noteworthy cata-
lyst, judging from its yield (49%), which was higher
than that of SO4 /ZrO2 -3 (25%).
The products were o-, m-, and p-methylbenzo-
phenones, and the distribution was not varied much:
2030% o-, 24% m-, and 7080% p-isomers. The
predominant p-substitution is similar to that by the
usual homogeneous reaction. An experimental homo-
geneous reaction using benzyl chloride and AlCl3
gave the isomeric composition of 13% o-, 3% m-, and
84% p-methylbenzophenones, the o-substitution over
the present catalysts being close to double.
Silicaaluminas, zeolites, and mordenites were
almost inactive for the reaction, even a famous ze-
olite, ZSM-5 (JRC-Z5-70H), being not active at
all. These materials hold acidities enough to cause
the FriedelCrafts reactions, and their acidities are
known to be in the range of superacidity [16]. The
acid strength was examined by the visual color
change method of the Hammett indicators; the indi-
cators were adsorbed on the solid surface in dried
cyclohexane at room temperature [7,9]. Zeolite-1
changed the basic forms (colorless) of p-nitrotoluene
(pKa = 11.35), p-nitrochlorobenzene (12.70), and
218 K. Arata et al. / Applied Catalysis A: General 197 (2000) 213219

m-nitrochlorobenzene (13.16) to the conjugate acid

forms (yellow), but did not change the color of
2,4-dinitrotoluene (13.75). Thus, the acid strength
is estimated to be 13.75 < Ho 13.16. Similarly,
the strength of moldenite-1 was determined to be
16.04 < Ho 14.52, that of silicaalumina-1 be-
ing 12.7 < Ho 11.35. Since acids stronger than
Ho = 12 are superacids, these solids are superacids.
However, zeolites are composed of Brnsted acid
sites, and this is the point of their inactivity.
In order to know whether Brnsted acid is inac-
tive for the acylation or not, several catalysts given
in Tables 13 were examined in the cracking of
cumene into benzene and propylene, a well known
reaction catalyzed by Brnsted sites. The reactivity
was, however, too high to compare the conversions,
and the decomposition of ethylbenzene into benzene
and ethylene was also too reactive. Thus, the dis-
proportionation of toluene into benzene and xylenes
was taken. Determination of the catalytic strengths
was tried by temperature/conversion comparisons
of silicaalumina-1, zeolite-1, and mordenite-1 with
WO3 /ZrO2 -3 and SO4 /ZrO2 -3; the results are shown
in Fig. 1. The temperature difference to show 5% con-
version among the catalysts is coincident with the acid
strength determined by the color change method of
the Hammett indicators: Ho < 16.04 for SO4 /ZrO2
and 16.04 < Ho 14.52 for WO3 /ZrO2 [9].

Fig. 2. Relation between the yields in the benzoylation and

the highest acid strength (Ho) of sulfated and supported metal
Fig. 1. Comparison of the activities of SiO2 Al2 O3 -1 (),
zeolite-1 (), and mordenite-1 () with those of SO4 /ZrO2 -3
() and WO3 /ZrO2 -3 () for the reaction of toluene.
oxides. () SO4 /SnO2 , () SO4 /ZrO2 -2, () SO4 /HfO2 , ()
WO3 /ZrO2 -3, (4) SO4 /TiO2 , (5) SO4 /Al2 O3 , () WO3 /TiO2 ,
() MoO3 /ZrO2 -3, () SO4 /Fe2 O3 , () B2 O3 /ZrO2 -3.
Fig. 1 as well as the results in the benzoylation indi-
cate that the inactivity of aluminosilicates for the acy-
lation is based on their catalytic action by Brnsted
acid sites. SO4 /ZrO2 is characterized to hold both
Lewis and Brnsted sites [1724]. SO4 /Al2 O3 was
recently reported to have both sites [25].
Although the Lewis acid strength as well as its vol-
ume of the present catalysts were not determined, a
relation between the acid strength and the yield in the
benzoylation was examined. The highest acid strength
(Ho) of sulfated and supported metal oxides was de-
termined by TPD using pyridine as well as by the
color change method using the Hammett indicators
 K. Arata et al. / Applied Catalysis A: General 197 (2000) 213219
Fig. 3. Yields in the acetylation of toluene with acetyl chloride
over SO4 /ZrO2 -1 at various temperatures.
[10]. Thus, the Ho values in the literature were plot-
ted with the yields in Tables 1 and 2; a roughly linear
relation was obtained as shown in Fig. 2, showing the
relationship between the acidity and the yield in some
degree.
Since satisfactory results were obtained in the
benzoylation, several catalysts were examined in the
acetylation of toluene, one of the difficult acylations
because of the difficulty in the formation of an in-
termediate acetyl cation (RCO+ ) from alkyl chain
acid anhydrides and halides. As shown in Table 3,
SO4 /ZrO2 -1 and PtSO4 /ZrO2 -3 gave 7% yield in the
reaction with acetic anhydride at 100 C for 3 h, 3%
by WO3 /ZrO2 -3.The acetylation was also performed
with SO4 /ZrO2 -1 and acetyl chloride as the acetylat-
ing reagent. The boiling point of acetyl chloride is
55 C. Thus, the reaction was inevitably carried out at
the temperature in an open reactor, but the yield was
below 2% at 50 C. The reaction mixture was heated
at temperatures above 80 C; the yield was found to
increase. The yields at 55, 80, 100, and 110 C were
plotted with the temperatures; a linear relation was
obtained, as shown in Fig. 3. Fig. 3 shows that the
heterogeneously adsorbed acetyl species is activated
to acetylation at the respective temperatures. As per
this point of view, we can conclude that the acety-
lation is possible at high temperatures in a closed
reactor such as an autoclave.
219
Acknowledgements
The authors thank Professor Makoto Hino, Hako-
date Technical College, for kindly providing us with
samples of PtSO4 /ZrO2 -3 and RuSO4 /ZrO2 -3.
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