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Eprints ID: 5817

To link to this article: DOI:10.2202/1542-6580.2183

URL: http://dx.doi.org/10.2202/1542-6580.2183

To cite this version: Aribert, Nicolas and Camy , Séverine and Lucchese,
Yolande and Condoret, Jean-Stéphane and Cognet, Patrick (2010) Cleaner
Routes for Friedel-Crafts Acylation. International Journal of Chemical
Reactor Engineering, vol. 8 (n°1). pp. A53 ISSN 1542-6580

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Cleaner Routes for Friedel-Crafts Acylation
Nicolas Aribert∗ Severine Camy† Yolande Peres Lucchese‡
Jean-Stéphane Condoret∗∗ Patrick Cognet††

∗
Ecole Nationale Supérieure des Ingénieurs en Arts Chimiques Et Technologiques, nico-
[email protected]
†
Ecole Nationale Supérieure des Ingénieurs en Arts Chimiques Et Technologiques, sever-
[email protected]
‡
Ecole Nationale Supérieure des Ingénieurs en Arts Chimiques Et Technologiques,
[email protected]
∗∗
Ecole Nationale Supérieure des Ingénieurs en Arts Chimiques Et Technologiques,
[email protected]
††
Ecole Nationale Supérieure des Ingénieurs en Arts Chimiques Et Technologiques,
[email protected]
 Cleaner Routes for Friedel-Crafts Acylation
Nicolas Aribert, Severine Camy, Yolande Peres Lucchese, Jean-Stéphane
Condoret, and Patrick Cognet

Abstract
Friedel-Crafts acylation is among the most fundamental and useful reactions
to yield aromatic ketones but it is one of the less acceptable in terms of unwanted
polluting by-products or atom economy because of the overconsumption of cata-
lyst which is used in stoichiometric quantities in the conventional process. This
route is nevertheless widely used in the fine chemical industry.

In recent years, awareness of the impact of industrial activities on the environ-

ment has led chemists to work on new chemical routes, less dangerous and more
environmentally friendly.

We considered here the acylation of a benzofurane derivative by an acyl chloride,

as an intermediary step for a pharmaceutical product. In this study, one of the first
alternatives was to replace conventional catalysts (FeCl3 or AlCl3 ), by reusable
solid catalysts. Indeed, a wide variety of new solid catalysts, more efficient and
less polluting, has now emerged (zeolites, ion-exchange resins. . . ). In this work,
these catalysts were first tested in “conventional” conditions, i.e., using an organic
solvent (1,2-dichlorobenzene in our case), to determine the best one, in terms of
reactivity, lifetime and reusability. The zeolite Y was found the most appropriate.

However, the use of an organic solvent still remains questionable and the use
of supercritical carbon dioxide as the solvent was also considered. Its inherent
properties include non-flammability, mild critical conditions, tuneable solubility
near to the critical point and very low environmental impact. The reaction was
operated using a continuous high pressure fixed bed. Results concerning yield
and selectivity are presented.

KEYWORDS: supercritical CO2 , Friedel-Crafts acylation, heterogeneous catal-

ysis, zeolite
1. INTRODUCTION
The Friedel-Crafts acylation of aromatic compounds is a major route for the
synthesis of aromatic ketones. This reaction is an electrophilic substitution by
acyl halides, anhydrides, carboxylic acids or esters with an aromatic substrate and
is conventionally carried out using over-stoichiometric amounts of metal halides
as catalysts. Despite the high production of unwanted polluting and corrosive by-
products (HCl in this case), Friedel-Crafts chemistry is widely used in the
manufacture of fine chemicals intermediates (pharmaceuticals, agrochemicals and
fragrances) (Gore, 1964).
In recent years, the concept of “green chemistry” has lead chemical
industries to develop new products, materials and chemical processes, less
dangerous and more environmentally friendly.
In the case of Friedel-Crafts acylation, a major drawback is linked to the
use of homogeneous polluting catalysts (Lewis acids: AlCl3, BF3, ZnCl2... or
Brønsted acids: H2SO4, HF ...) and alternative routes using solid catalysts (Corma,
1995; Jasra, 2003) are to be found). Nowadays, a wide variety of solid catalysts,
more efficient and less polluting can be proposed, such as zeolites, ion exchange
resins, heteropolyacids... Such solid catalysts can be easily separated from liquid
products and, in addition, they offer the possibility of carrying out Friedel–Crafts
reactions using a continuously operated fixed-bed reactor, rather than batch
reactors. For the same production target, continuous flow reactors have smaller
size than batch reactors, thus increasing safety and reducing capital cost.
The second drawback is related to the use of organic solvents, potentially
toxic or polluting. Carbon dioxide used as the reaction solvent can be a good
alternative to conventional organic solvents, because, in this case, it has no
environmental impact. Its usefulness particularly in the field of chemical
synthesis has been now amply demonstrated (Beckman, 2004; Rayner, 2007;
Ghosh et al., 2005; Patcas et al. 2007, Arunajatesan et al., 2001; Hitzler et al.,
1998).
This article presents first experimental results obtained for a Friedel-Crafts
acylation reaction using new kind of catalysts in supercritical carbon dioxide. The
first part of this work has consisted in the determination of the most appropriate
solid catalyst in terms of yield and selectivity of the reaction, using
dichlorobenzene as the solvent. Secondly, a transposition of the reactants/solid
catalyst system has been done using supercritical CO2 as the solvent and the
reaction has been operated in a continuous high-pressure fixed-bed reactor.
2. EXPERIMENTAL

2.1 Materials
Different kinds of catalysts can be used to perform Friedel-Crafts acylation:
zeolites, ion exchange resins, metallic oxides, heteropolyacids (HPA) and clays.
This preliminary choice of catalyst was made according to their reported
efficiency for different aromatic acylations (Jasra, 2003; Arata et al., 2000;
Choudhary et al., 2000).
Zeolites types H-BEA, H-Y and H-MOR have been investigated for this
reaction. Zeolites H-Y with SiO2/Al2O3 molar ratios of 6, 15 and 200 and zeolites
H-BEA with SiO2/Al2O3 molar ratios of 27 were purchased from Tosoh as
powder. Zeolite H-Y (SiO2/Al2O3 = 15) was also purchased in pellet form (1.5mm
diameter and 2-5mm length cylinders). Zeolite H-MOR with SiO2/Al2O3 molar
ratio of 12 was supplied by Tricat Zeolites GmbH. Amberlyst-15 (ion-exchange
resin), phosphotungstic acid (HPA) and Montmorillonite K-10 (Clay) were all
purchased from Sigma-Aldrich. All these catalysts were in their acidic H-form.
The activation of the zeolites is done by calcination using the following
procedure: the sample of catalyst is heated in a furnace with a heating rate of 4
°C.min-1 from room temperature to 500°C and then maintained at this temperature
during 6 hours
The metallic oxides (Ga2O3, Bi2O3, Fe2O3 and In2O3) were obtained from
Sigma-Aldrich.
The water content of solvents (1,2-dichlorobenzene and CO2) has to be as
low as possible to avoid the degradation of the acyl chloride into the
corresponding acid and HCl. 1,2-dichlorobenzene (anhydrous) was purchased
from Sigma-Aldrich and CO2 (water content < 7 ppm) was supplied by Air
Liquide.
In the context of this study, which is done through a collaborative
industrial contract, it is not possible to disclose the exact name of the involved
molecules. Figure 1 shows the reaction scheme: the substrate (a benzofuran
derivative) is acylated by an aromatic chloride.
R2
O
O
Catalyst
R1 n-Bu + R1 HCl
O R2 Cl
n-Bu +
O
Substrate Acyl chloride Product
S AC P
Figure 1. Reaction scheme
This lack of information about the involved molecules is not detrimental to the
scientific aspect of the work, where this reaction is a model reaction to illustrate
the concept of improving this kind of Friedel-Crafts type reaction.

2.2 Reaction procedure

2.2.a Operation using a conventional organic solvent

The acylation reactions were carried out in a 250 mL batch reactor equipped with
a condenser and magnetic stirrer where the acyl choride (AC), the aromatic
substrate (AS) and the solvent (dichlorobenzene, S) were mixed inside the
reactor. The different catalysts (note that in the case of zeolites, they were used
directly after calcination) were then introduced into the reactor and the medium
heated up to the reaction temperature. The resulting suspension was stirred under
reflux for 6h.
Samples were taken periodically during the reaction with a syringe and
assayed by HPLC (Waters 600E apparatus with Symmetry C8 column).

2.2.b Operation using supercritical CO2

The catalytic acylation reactions in supercritical conditions were performed in a

continuous fixed-bed reactor, consisting of: (i) a supply unit, (ii) a reaction unit
and (iii) an analytical loop (Fig. 2).
The supply unit comprised two HPLC pumps, one for the reactant liquid mixture,
at a given ratio AS/AC, and one for liquid CO2. A static mixer (heated around
60°C) before the reaction unit allows good mixing of reactants and CO2.
The reaction unit comprised a tubular reactor with an internal cartridge
(14mL cylinder, 0.50m length, 6mm inner diameter, closed by 3 µm fritted disks)
filled with the solid catalyst, a safety rupture disc, a pressure transducer and a K-
type thermocouple located inside the catalytic bed, near the outlet. Operation at
the desired temperature, up to 500°C, is done using electrically heated shells
around the tube, coupled to a PID temperature controller. The pressure is set
using a mechanical back pressure regulator. The complete reaction unit was
provided by Top Industrie, France.
Our system allows in-situ calcination of the catalyst. The calcination step
is performed at 500°C during 6 h under air sweeping at a flow-rate of 250
mL.min-1 (STP).
 TCI (PID) Vent

PI
Static Mixer

Air
Compressed
air

Cooling
Fixed-bed
Reactor Bubble
HPLC
Flowmeter
Pump
CO2

Regulator
back pressure
HPLC Pump

Reactants TI

Loop
Purge

HPLC pump Purge

Analysis solvent

Figure 2. Scheme of the high pressure fixed bed (length 50 cm, inner
diameter 6mm)

Continuous reactors for supercritical fluids offer the advantage over batch
reactors that they do not require depressurisation to feed the reactants or to
recover the products. In our system, samples can be taken out periodically during
the reaction by using a sample loop of known volume. The obtained sample is
then depressurized into the HPLC solvent and the loop is rinsed with 10 loop
volumes of solvent. The HPLC analytic apparatus and procedure are the same as
for the reaction in conventional solvent.
The procedure for operation of the continuous high pressure reaction is as
follows:
- The cartridge is loaded with 4.3g of catalyst and calcined following the
already described calcination procedure.
- Then the CO2 is pumped to pressurize the system, and pressure is
controlled by the back pressure regulator. The reactor is then heated up in
the range 150-180°C, depending on experiments. When the temperature in
the fixed bed is stabilized at the desired value, the mixture of the reactants
is pumped into the CO2 flow. Samples are taken at 30 min time intervals.
 The flow of CO2 was fixed to 1g.min-1 or 2g.min-1, and the flow of
reactants to 0.1g or 0.05g depending on experiments. The pressure was
fixed at the technical maximum value of 300 bar, to minimize the loss of
dissolving power of CO2, induced by the high temperature needed for the
reaction.

3. RESULTS AND DISCUSSION

3.1 Operation in dichlorobenzene

Table 1 presents the results of acylation performed in dichlorobenzene as the

solvent over various solid acid catalysts at 180°C. Among these different kinds of
catalysts, zeolite Y and Indium oxide appear to be the most efficient. Conversely,
K-10 clay, HPA and H-Mor proved to be completely inactive, since no trace of
product has been detected. Zeolite !, Amberlyst-15, bismuth oxide and iron oxide
were found barely active.

Table 1: Acylation yields using different types of solid acid catalysts (10
mmol of AS; 10 mmol of AC; 50mL of dichlorobenzene, catalyst loading
1.0g, temperature 180°C)
Catalyst loading Surface area
Catalyst (SiO2/Al2O3) Yield (time)
(g) (m2/g)
330 HUA H-Y(6) 1 550 18% (6h)
360 HUA H-Y(15) 1 600 45% (6h)
390 HUA H-Y(200) 1 750 1% (6h)
930 NHA H-! (27) 1 630 4% (6h)
TZM-1013 H-Mor (12) 1 475 NPDa (6h)
Resin Amberlyst-15 1 53 6,3% (6h)
HPA H3[P(W3O10)4] 1 4.6 0,2% (6h)
Ga2O3 1 10-50 16,3% (3h)
1 44,1% (3h)
In2O3 25-50
Oxide 0.1 42,2% (3h)
Fe2O3 1 30-50 6,5% (3h)
Bi2O3 1 10-50 1,6% (3h)
Clay Mont. K-10 1 220 NRb (6h)
a
NPD: No product detected
 Table 1 indicates a very good activity for indium oxide, the yield being
around 42% after 3 hours of reaction, even with a smaller amount of catalyst
(0.1g), but reusability tests were not satisfactory. Indeed, it was not possible to
recover the solid which seemed to have been solubilized in the medium of
reaction.
So, zeolite Y (15) appears to be the best solid catalyst for this acylation
reaction because high yields were obtained (45%) and no recovery problems have
been observed. Note that the ratio SiO2/Al2O3 of the zeolite plays an important
role because 6 and 200 ratios gave lower yields (respectively 18% and 1%).
Before operating this catalytic system in a continuous supercritical fixed-
bed reactor, some additional experiments in dichlorobenzene were necessary to
approach optimal operating conditions of the reaction. So AS/AC ratio, catalyst
loading and catalyst reusability were further investigated. Indeed, preliminary
results have shown that the maximal yield reaches 80% with 2g of zeolite Y (15)
during 6 hours and that the reactant ratio is the main parameter, as shown on
figure 3.

100%

80%
Yield (%)

60%

40%

20%

0%
0 60 120 180 240 300 360
Time (min)

Figure 3. Effect of AS/AC ratio on yield (10mmol of AS; 10-100 mmol

of AC; 50mL of dichlorobenzene; catalyst loading 2,0g; temperature
180°C),! ratio 1/1," ratio 1/1.5,+ 1/4, "#ratio1/10

The best yield has been obtained for an AS/AC ratio equal to 1 mol of
substrate for 1.5 mol of acylating agent. Results are similar when the ratio AS/AC
is increased to 1/4. But using a great excess of AC (ratio 1/10) seems to inhibit
the activity of the zeolite. One hypothesis could be that active sites are saturated
by the AC. In fact this inhibition could also have been detected at the end of the
curve with a ratio of 1/4 (around 4h) where kinetics stabilize unlike the
experiment carried out with a 1/1.5 ratio, where kinetics slow down but do not
stop. During these different experiments few by-products were generated. The
only detected one was the anhydride form of the AC, which could be easily
eliminated by simple post-reaction hydrolysis of the medium.
Another key parameter for industrial development deals with the
reusability of the catalyst. After a single use and reuse after filtration on a fritted
disc only, the yield drops significantly from 80 to 18% (see figure 4). The main
reason of this deactivation phenomenon of the zeolite may be the deposition of
heavy products, usually termed as “coke”. According to Richard et al. (1995) this
“coke” probably results from the acylation of compounds obtained by
condensation of aromatic substrates, thus blocking the actives sites. Figure 4 also
shows that the calcination of the used zeolite allows complete recovery of its
catalytic activity. Indeed, the need for zeolite regeneration was already observed
by Guignard et al. (2002) and Moreau et al. (2000). So the efficiency of
regeneration (here by calcination) of the catalyst becomes a prominent parameter.

100%

80%
Yield (%)

60%

40%

20%

0%
0 60 120 180 240 300 360
Time (min)

Figure 4. Reusability of zeolite Y (10mmol of AS; 20 mmol of AC;

50mL of S; catalyst loading 2,0g; temperature 180°C), × “fresh” calcined
zeolite, reused zeolite, ! zeolite once regenerated, # zeolite twice
regenerated, $ zeolite three times regenerated
 Finally, these experiments using a conventional organic solvent have
indicated that zeolite Y (15) is a suitable solid catalyst for the acylation reaction
of the substrate. The next step of our study consists now in replacing
dichlorobenzene by supercritical CO2, using zeolite Y (15) as the catalyst. To do
so, a fixed-bed reactor has been designed in order to run the reaction in a
continuous process.

3.2 Supercritical conditions

First experiments on the continuous set-up have been done with zeolite Y (15) in
its powder form. Preliminary calculations, using Darcy’s law, have estimated that
the expected pressure drop in these conditions would be equal to 16 bar with a
powder granulometry around 6-8$m, and this value was found to be acceptable
for an operating pressure above 200 bar. Experiments confirmed the value of the
predicted pressure drop.
However use of zeolite powder proved to be very problematic, because all
reaction runs ultimately led to clogging of the reactor, probably because the
catalyst particles were indeed too small to be used in the fixed-bed reactor.
Although duration of the experiments were not sufficient to be really
representative because of clogging after a few hours, a 10% yield was typically
observed (2g.min-1 of CO2, 0.05g.min-1 of reactants with a ratio AS/AC=1/2,
T=180°C, P=200 bar).
Fortunately, zeolite H-Y (15) was also available in pellet form: 1.5 mm
diameter and 2-5mm length cylinders, containing 20% of inactive binder clay
(“Montmorillonite K-10”). Use of these pellets did not lead to clogging of the
reactor. The pressure drop of the bed of pellets is expected to be much smaller
and the observed pressure drop was mainly due to the 3 µm fritted disks at the
ends of the tube, and did not exceed 5 bar.
Figure 5 presents the time course of the product concentration at the
output of the fixed bed obtained using the sample loop. Note here the influence of
the calcination pre-treatment where 15% yield, compared to 5% using fresh non
calcined zeolite, is observed. Figure 5 also shows that the yield at the output
declines rapidly after 60 minutes (maximal yield reached at this value of time).
 30%

20%
Yield (%)

10%

0%
0 60 120 180 240 300 360
Time(min)

Figure 5. Yield of product with zeolite Y (15) in pellet form (2g/min of

CO2, 0.05g/min of reactants with a ratio AS/AC=1/2, T=150°C,
P=300bar), × non-calcined zeolite, " calcined zeolite

As a first hypothesis, these poor yield values could be attributed to the low
solvating power of CO2 in respect to reactants and/or products. Indeed, it is well
known that the solvent power of pure CO2 is low in respect to high molecular
weight compound, as it is the case here.. Moreover, to insure significant activity
of the catalyst, the temperature must be very high, and in spite of the high
pressure in the process, this is not very favourable for a good solubility of the
reactants and products in CO2. A comprehensive analysis o reactant solubility for
the case of hydrogenation in supercritical solvents can be found in Pereda et al,
(2002).To overcome this possible limitation, operation in mixtures of
dichlorobenzene and CO2 was considered. Figure 6 presents the computed phase
diagram of the mixture dichlorobenzene-CO2 at 150 °C. These results have been
obtained using the Peng Robinson equation of state (PR EOS) with the value of
binary interaction parameter k12 = 0.1175 (from Stüber et al. (1996)).
Computations were made using the Simulis software (ProSim S.A., France). This
diagram shows that, at 150 °C and 300 bar, two kinds of mixtures are possible
depending on the composition: for CO2 mass fraction lower than 0.43, a low
density liquid exists. Conversely, for CO2 mass fraction higher than 0.71, the
mixture is a dense gas. Between these two values, the mixture is a biphasic
system.
 400

300
L V
Pressure ( Bar )

L-V
200

100

0 0.43 0.71
0 0.5 1
Mass Fraction of CO2

Figure 6: Isothermal fluid phase equilibrium diagram for T = 150°C

System: dichlorobenzene-CO2 (computed using Peng Robinson EOS and
interaction parameter k12=0.1175 (value of k12 from Stüber et al., 1996))

From this phase diagram, we performed the reaction in the two single-
phase domains: the dense gas (CO2 rich) and the expanded liquid
(dichlorobenzene rich). Experimental results are presented on figure 7. Using a
low mass fraction of CO2 (CO2 mass fraction = 0.37, density = 1060 g/L,
calculated with Peng Robinson EOS) no product was detected, whereas, with a
homogeneous dense vapour phase of CO2 enriched with DCB (CO2 mass fraction
= 0.72, density = 880 g/L, obtained with Peng Robinson EOS), a maximum 15%
yield was obtained, despite occurrence of a rapid deactivation of the catalyst. This
deactivation phenomenon seems to be slower with pure carbon dioxide. Note that
in these experiments the zeolites have not been pre-treated by calcination
 30%

20%
Yield (%)

10%

0%
0 60 120 180 240 300 360
Time (min)
Figure 7: Yield of the product using H-Y zeolite in pellet form
(0.05g/min of reactants with a ratio AS/AC=1/2, T=150°C, P=300bar), !
1.92 g/min of dichorobenzene-CO2 (CO2 mass fraction 0.37), " 1.8 g/min
of dichorobenzene-CO2 (CO2 mass fraction 0.72), × 2 g/min of pure CO2.

4. CONCLUSION
From experiments in a conventional organic solvent (1-2 dichlorobenzene),
zeolite Y (15) proved to be the more appropriate solid catalyst for the Friedel-
Crafts acylation of a benzofurane derivative by an acid chloride. The different
experiments carried out with zeolite Y (15) have given promising results, where
few by-products were generated. The only detected one was the anhydride form
of the AC, which could be easily eliminated by simple post-reaction hydrolysis of
the medium.
In order to propose a cleaner process, with reduced use or total absence of
an organic solvent, the reaction was tested in a continuous fixed bed reactor using
supercritical carbon dioxide, or mixtures of carbon dioxide and dichlorobenzene,
as the solvent. These experiments yielded interesting and encouraging results,
even if rapid deactivation of the zeolite was observed. Note that a specific
formulation of the catalyst, i.e., under pellet form, was necessary to operate the
fixed-bed reactor without clogging. The deactivation phenomenon still need to be
understood and might be improved by varying temperature or pressure. Although
incomplete, these works are preliminary works to investigate new cleaner routes
for this kind of chemistry and have demonstrated the feasibility of the approach.
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