Ind. Eng. Chem. Res.

2007, 46, 8657-8664 8657

Eco-friendly, Selective Hydroxylation of C-7 Aromatic Compounds Catalyzed by

TS-1/H2O2 System under Solvent-free Solid-Liquid-Liquid-Type Triphase
Conditions
P. Mukherjee,† Asim Bhaumik,‡ and Rajiv Kumar*
Catalysis DiVision, National Chemical Laboratory, Pune-411 008, India

Direct ring hydroxylation of aromatics, namely, anisole, toluene, and benzylchloride, using TS-1 catalyst, a
MFI-type titanium silicate molecular sieve, dilute H2O2 as oxidizing agent, and water as reaction medium,
was investigated under solid-liquid-liquid (SLL)-type triphase conditions. The aim was to study the relative
influence of commonly used organic solvents, under solid-liquid (SL)-type biphase reaction conditions, as
compared to that of water, on the conversion and product selectivity. Under solvent-free triphase conditions,
the ring hydroxylation of anisole, toluene, and benzylchloride leads to significant enhancement in the conversion,
turn-over frequency, and para-selectivity. However, in the case of benzyl chloride, no ring hydroxylation
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took place under biphase conditions (using acetone as solvent) contrary to significant ring hydroxylation (ca.
60% H2O2 efficiency) under triphase aqueous medium conditions. The simple product recovery (phase
separation of organic and aqueous layers) and use of water as reaction medium are other advantages. Since
TS-1 is relatively hydrophobic, the reaction is hindered in the presence of organic solvents as they compete
favorably with the substrate for diffusion inside the TS-1 channels. However, in the presence of water, the
organic substrate competes favorably with water, leading to increased conversion and para-selectivity.

1. Introduction dation of olefins and allylic alcohols to corresponding epoxides,

One of the major problems encountered in liquid-phase
heterogeneous catalytic systems, using either (i) homogeneous
catalyst and two immiscible liquids (liquid-liquid, LL) where
catalyst is soluble in at least one liquid phase or (ii) heteroge-
neous catalyst along with two immiscible liquid phases (solid-
liquid-liquid, SLL), is mutually immiscible reagent and sub-
strate due to phase boundaries. If the reaction occurs at liquid-
liquid-phase boundary, rapid stirring may help in facilitating
the reaction. However, most commonly either an organic cosol-
vent or a phase-transfer catalyst is used to remove phase
boundaries and thereby facilitate the reaction. However, the use
of organic solvents as well as phase-transfer catalysts poses
major problems in downstream processing. Further, the use of
organic solvents causes environmental concerns also and is
thereby against the principles of green chemistry. Hence, the
organic transformations under either solvent-free conditions or
in the presence of water as reaction medium are attracting
increasing attention. However, from the practical point of view,
the green chemical processes should also favorably compete
economically with enhanced yield of desired product and reduce
the cost of downstream workup and product recovery.
Zeolites and their metallosilicate analogs, also known as
microporous molecular sieves, are an important class of solid
catalysts used in several industrial processes in the areas of oil
refining, petrochemicals, bulk chemicals, and, more recently,
specialty/fine chemicals.1,2 TS-1, a titanium silicate having MFI
topology (Mobils FIve, IUPAC nomenclature), has been found
to be an excellent oxidation catalyst using environmentally
benign hydrogen peroxide as oxidizing agent for a variety of
oxidation reactions such as hydroxylation of aromatics, epoxi-
* Corresponding author. Tel.: +91-20-2590 2631. Fax: +91-20-
25902633. E-mail: r.kumar@ncl.res.in.
† and hydroquinone, respectively, where the methylating agent
Present address: Biomedical Engineering, Mayo Clinic, Rochester,
MN 55905.
‡
Present address: Department of Materials Science, Indian Associa-
tion of Cultivation of Sciences, Kolkata, India.
10.1021/ie070088q CCC: $37.00 © 2007 American Chemical Society
Published on Web 10/27/2007
oxy-functionalization of alkanes, oxidation of organic sulfides
to sulfones and sulfoxides, etc.3-6
The nature of the solvent used significantly influences the
activity and selectivity in the oxidation reactions catalyzed by
the TS-1-H2O2 catalytic system. Quite interestingly, our
preliminary results on the use of water as reaction medium in
the direct hydroxylation of aromatics like benzene, toluene,
anisole, and m-cresol,7,8 as well as detailed studies on benzene
to phenol,9,10 catalyzed by TS-1 and dilute H2O2 under solid-
liquid-liquid (SLL) triphase conditions suggest that the sig-
nificantly higher conversions can be achieved in triphase
conditions (compared to that in SL biphase conditions using
organic solvents) mainly because of the hydrophobic nature of
TS-1. Because of this, the organic substrate like benzene
competes more favorably with water (in triphase) than with
organic solvent (like methanol or acetone) for diffusion to the
active sites mainly situated inside the channels of TS-1, thereby
resulting in increased conversion. Another advantage of this
approach is that it features quite simple downstream processing
where unconverted reactant and products are simply phase
separated. The aqueous phase along with catalyst can be recycled
and reused after required water stripping to avoid any buildup
of water, which is coproduced during the hydroxylation reaction
using dilute aqueous H2O2 as oxidizing agent. This approach
fits very well for developing green catalytic processes, which
is of paramount importance for the chemical transformations.11
The direct hydroxylation of aromatic in general and of anisole
in particular is of high importance from an industrial point of
view also. Both the ortho-hydroxyanisole, O-HA (commonly
known as guaiacol), and para-hydroxyanisole, P-HA (commonly
known as monomethoxyhydroquinone), are value-added prod-
ucts of anisole and are produced via O-methylation of chatechol
used can be selected from dimethyl sulfate, dimethyl carbonate,
or methanol (Scheme 1, route A). However, the selectivity
toward monomethylated products is a major issue for this route
8658 Ind. Eng. Chem. Res., Vol. 46, No. 25, 2007
Scheme 1: Hydroxylation of Anisole
Scheme 2: Hydroxylation of Toluene
because the formation of secondary di-O-methylated products,
i.e., dimethoxy benzene, needs to be avoided. However, the
direct hydroxylation of anisole, which is manufactured by the
O-methylation of phenol, can selectively produce O-HA and
P-HA (Scheme 1, route B). In this case, the question of
dimethoxy benzene formation does not arise, thereby resulting
in high selectivity for desired products.
Both the o-cresol and the p-cresol are also industrially
important chemicals and are produced by ring methylation of
phenol. Direct hydroxylation of toluene is an attractive and quite
challenging route for the preparation of cresols. As shown in
Scheme 2, in the case of toluene, there are two oxidation sites
viz. (i) the primary carbon atom of the side-chain methyl group,
leading to the formation of benzyl alcohol, benzaldehyde, and
benzoic acid, and (ii) the aromatic ring to produce cresols. Using
hydrogen peroxide as oxidizing agent, the side-chain oxidation
is mainly catalyzed by OH• radical species due to homolytic
cleavage of H2O2; the aromatic ring hydroxylation may proceed
via heterolytically cleaved ionic HOO- species.3-5 It is of
significant interest to study the relative role played by the radical
and ionic routes in the case of toluene hydroxylation in biphase
(using organic solvent) and triphase (using water as reaction
medium). In order to further probe this aspect, the hydroxylation
of benzyl chloride was considered worthwhile for oxidation
studies. Benzyl chloride provides an additional possibility for
oxidation/hydrolysis. Further, the hydroxylation of the aromatic
ring of benzyl chloride will be partially deactivated (contrary
to toluene and anisole), thereby lowering selectivity for valuable
o-hydroxybenzychloride and p-hydroxybenzylchloride vis-à-vis
side-chain oxidation, followed by HCl removal to form ben-
zaldehyde and benzoic acid.
The present manuscript reports detailed studies on the direct
hydroxylation of C-7 aromatics (substituted benzenes) like
toluene, anisole, and benzylchloride, where the inductive
influence of the substituent group in the aromatic ring on the
activity and product selectivity is studied systematically using
TS-1 as catalyst and dilute hydrogen peroxide (35 wt % aq.)
under SLL triphase conditions in the presence of water as
reaction medium. For comparative purposes, the data obtained
under SL biphase (using organic cosolvent) are also presented.
The effects of various reaction parameters like temperature, time,
substrate-to-catalyst ratio, substrate-to-H2O2 molar ratio, dilution,
and stirring rate on the conversion as well as product distribution
including isomer distribution (regioselectivity) are reported.
Further, in order to understand the reaction path (radical versus
ionic) in biphase and triphase, competitive oxidation using
cyclohexane as cosubstrate and control experiments in inert
atmosphere using nitrogen (both under flow and static nitrogen
blanket) were also conducted.
2. Experimental Section
2.1. Synthesis. The TS-1 samples with three different Si/Ti
molar ratios were prepared according to our published proce-
dure.8,12 Three samples with different Si/Ti molar ratios (sample
A, Si /Ti ) 33; sample B, Si /Ti ) 58; and sample C, Si/Ti )
80) were synthesized hydrothermally at 433 K. In a typical
synthesis of sample A, as an example, 21.0 g of TEOS (tetra-
ethyl orthosilicate, Aldrich, 98.5%) was added under stirring
to 40.6 g of TPAOH (tetrapropylammonium hydroxide, 20% aq.,
Aldrich), and the stirring was continued for 1 h. Then 1.13 g of
TNBT (tetra-n-butyl titanate) in 5.0 g of dry IPA (isopropyl
alcohol) was added slowly to the above reaction mixture and
again allowed to stir for 1 h. Finally, 0.77 g of H3PO4 (phos-
phoric acid, 85% aq., sd fine chem., India) in 19.7 g of water
was added to the above mixture slowly and allowed to stir for
1 h more. The solution thus-obtained was autoclaved at 433 K
for 6 h. For all three samples, the pH of the initial synthesis
mixture (clear solution) was found to be 11.5 ( 0.1, and the
corresponding value after the completion of the crystallization
was 12.2 ( 0.1. For samples B and C, 0.60 g of TNBT in 5 g
of IPA, and 0.42 g of TNBT in 5 g of IPA, respectively, were
taken, keeping all other ingredients same. The initial composition
of the synthesis mixture was as follows: 1TEOS/0.4TPAOH/
xTNBT/0.95IPA/0.067H3PO4/30H2O, where x was 0.030, 0.018,
and 0.013 for TS-1 samples A, B, and C, respectively. The solid
yield of recovered and calcined TS-1 material was ∼80 ( 2 wt
% on the basis of silica taken in the initial synthesis mixture.
The as-synthesized solid samples were recovered from the
mother liquor by centrifugation followed by thorough washing
with demineralized water, treating with 1 wt % aqueous solution
of ammonium acetate, washing thoroughly with a copious
amount of demineralized water, and drying at 120 °C in an oven.
The dried powder was then calcined at 550 °C in flowing air
for 16 h before use as a catalyst.
2.2. Catalyst Characterization. All three TS-1 samples
synthesized were characterized by well-known characterization
techniques such as X-ray diffraction (XRD), UV-vis, IR,
scanning electron microscopy (SEM), and energy-dispersive
X-ray spectroscopy (EDX). The XRD measurements of all the
samples were done in Rigaku D MAX III VC diffractometer
using Ni filtered Cu KR radiation (λ ) 1.5404 Å). UV-vis
spectra were recorded using a Shimadzu UV-vis spectrometer
(UV-2101 PC). The baseline correction was made using barium
sulfate as the standard. All spectra were recorded in the range
of 200-600 nm. The IR spectra were recorded on a Fourier
transform infrared (FTIR) spectrometer (Perkin-Elmer Series
1600) in the range of 400-1300 cm-1 using KBr pellet
technique. Scanning electron micrographs were obtained using
JEOL JSM 5200, operated at 20 kV. Elemental analysis was
performed through electron-probe microanalysis on an EDX
detector, KEVEX 7000 system. Catalyst samples were loaded
on a stub and coated with gold film before being scanned.
2.3. Catalytic Reactions. The liquid-phase catalytic reactions
were conducted in a magnetically stirred, three-necked glass
batch reactor where x mol of substrate and y mol of H2O2 (x/y

molar was in the range of 1:1 to 10:1) were reacted over z g of
catalyst, (TS-1, z ) 5-20 wt % with respect to the substrate)
in the absence of organic solvent (in solvent-free conditions)
where water was added for better dispersion of the catalyst in
the solid-liquid-liquid three-phase system or in the presence
of organic cosolvent (methanol, acetone, or acetonitrile) in SL
biphase conditions. However, the total mass of the reaction
mixture was kept the same in both cases. The products were
collected and analyzed by high-resolution gas chromatography,
GC (HP, 5880 and Shimadzu R-17A using a flame-ionization
detector (FID) and 50 m long capillary column coated with
silicon gum). In all cases, the standard compounds were used
to calculate the response factors for the reactant and all the
products for quantitative analysis.
The inert atmosphere reactions (static nitrogen) were carried
out in a glass batch reactor where the reactor was first flushed
with dry nitrogen followed by fitting of a nitrogen balloon on
the top of the condenser on a two-way stopcock. For flowing
nitrogen, the nitrogen was bubbled continuously through the
reaction mixture through a septum. The conversion of limiting
reagent hydrogen peroxide, referred as “H2O2 efficiency, mol
%” was calculated as follows: ((moles of total oxidation
products formed)/(total moles of H2O2 taken)) × 100. The total
products formed include secondary oxidation products also, if
any. For example, if x mol of benzaldehyde and y mol of benzoic
acid are formed in the oxidation of benzyl chloride, then the
mol of H2O2 consumed will be equal to 1x + 2y. Hence, in
such cases where secondary oxidation products are formed, the
sum of the total mol of H2O2 that got consumed toward the
formation of oxygenated products is taken for calculating the
H2O2 efficiency.
3. Results and Discussion
3.1. Characterization of Catalyst Samples (TS-1). Since
the details of the catalyst (TS-1) characterization are given in
our earlier paper,9 they are omitted from this manuscript.
However, for the sake of completeness, a summary of the
characterization details of three catalyst samples having three
different Si/Ti molar ratios is presented here. The Si/Ti molar
ratios in the solid were found to be 33, 58, and 80, respectively,
for TS-1 samples A, B, and C. All the samples were fully
crystalline, having MFI topology. The UV-vis spectra showed
an intense band centered at 210-215 nm, without any absorption
in the region of 280-340 nm, clearly suggesting the absence
of any extraframework penta- or hexa-coordinated Ti4+ spe-
cies.5,9 FTIR spectra of all three TS-1 samples showed a
characteristic 960 cm-1 band. As expected, the ratio of the
relative intensities of the 960 and 550 cm-1 bands decreased
with decreasing Ti contents in the sample, in accordance with
earlier reports.5 The crystallite size of TS-1 samples, obtained
from scanning electron microscopy, was in the range of 100-
200 nm, which is typical of a synthesis carried out in the
presence of promoter (H3PO4).12
3.2. Hydroxylation of C7 Aromatics (Substituted Ben-
zenes). 3.2.1. Hydroxylation of Anisole. The effect of different
solvents on the conversion of anisole, H2O2 efficiency (mol of
H2O2 consumed for the production of oxygenated products),
and selectivity in the direct hydroxylation of anisole is given
in Table 1. When acetone and methanol were used as the
solvent, the anisole conversion, H2O2 efficiency, and TOF were
also low and the selectivity for o-hydroxyanisole was higher
compared to that for p-isomer. When t-BuOH (t-butanol) was
used as the solvent, though the system is biphasic in nature,
p-hydroxyanisole was the major product. However, in triphase,
Ind. Eng. Chem. Res., Vol. 46, No. 25, 2007 8659
Table 1. Effect of Solvents/Dispersion Medium in the Hydroxylation
of Anisolea
product distribution, mol %
solvent/ anisole H2O2
dispersion conv.b effi.c TOF o-hydroxy- p-hydroxy-
medium (mol %) (mol %) (h-1) anisole anisole
water 14.5 72.5 11.5 25.0 75.0
methanol 9.0 45.0 7.2 60.0 40.0
acetone 7.0 35.0 5.6 55.0 45.0
t-butanol 3.0 15.0 2.4 24.0 76.0
a Reaction conditions: anisole/solvent or water ) 1:5 (wt/wt), catalyst
A (TS-1/33) ) 20 wt % with respect to anisole, anisole/H2O2 ) 5:1 (mol/
mol); temperature ) 80 °C; time ) 6 h; H2O2 was added in a lot under
vigorous stirring. b Conversion is based on the number of moles of H2O2
taken with respect to anisole. c H2O2 efficiency is defined as the number
of moles of H2O2 utilized for the formation of oxygenated anisole products.
both the conversion and the selectivity for p-hydroxyanisole
were significantly higher than that in the presence of organic
solvent. It is well-known that medium-pore MFI structure is
selective toward para-substituted products because of its pore
architecture. Hence, higher selectivity for p-hydroxyanisole is
expected in the hydroxylation of anisole, if the reaction is mainly
occurring inside the TS-1 channels. However, if the reaction is
mainly occurring on the nonselective external surface, then
o-hydroxyanisole would be the preferred isomer formed. The
observed high para-selectivity in the presence of water and
t-butanol as reaction medium clearly indicates that the hydroxy-
lation takes place inside the pores, while in the presence of
methanol or acetone, the reaction may be taking place consider-
ably on the catalyst’s external surface.
These interesting results obtained with different solvents with
different molecular dimensions support our view that, under
biphasic conditions, the organic solvent is the main adsorbate.
When the size of the solvent molecule increases, its diffusion
inside the catalyst channel is limited, and as a result, the
adsorption of the reactant becomes the predominant diffusion
phenomenon inside the TS-1 catalyst. The lower H2O2 efficiency
and TOF observed in the case of t-BuOH may be due to the
like-like interaction between anisole and the alcohol, which
might hinder the diffusion of anisole into the TS-1 channels.
All further experiments were carried out in solvent-free triphase
conditions using TS-1 as catalyst and dilute H2O2 as oxidant.
When the progress of the reaction was followed with time
during the hydroxylation of anisole under triphase over the TS-
1/H2O2 system (Figure 1), it was observed that the reaction is
reasonably fast from the very beginning. Both the H2O2
efficiency and, consequently, the anisole conversion gradually
increase with time and level off after almost 4 h. Further, with
the progress of the time, the selectivity for the p-isomer increases
slightly with the corresponding decrease in the selectivity for
the o-isomer. This may be because the density of surface-active
species is much less compared to the active sites inside the pores;
therefore, with reaction time, the rate of reaction inside the pores
increases, whereas the contribution of surface reaction remains
the same or may even decrease due to surface sites deactivation
or in other words “selective passivation” of catalytic sites located
at the external surface of TS-1 crystallites during the reaction.
Table 2 presents the effect of temperature on anisole
conversion and H2O2 efficiency in the formation of hydroxya-
nisole isomers. At room temperature, the H2O2 efficiency, TOF,
and p-hydroxyanisole selectivity were low. The selectivity for
p-isomer and the H2O2 efficiency increased with the increase
in temperature. At 80 °C, maximum H2O2 efficiency, TOF, and
p-hydroxyanisole selectivity were obtained, as expected. At
∼100 °C, the noncatalytic decomposition of H2O2 becomes more
8660 Ind. Eng. Chem. Res., Vol. 46, No. 25, 2007

Table 4. Effect of Anisole-to-H2O2 Molar Ratio in the

Hydroxylation of Anisolea
product distribution, mol %
anisole H 2O 2
anisole/H2O2 conv. effi. TOF o-hydroxy- p-hydroxy-
mol ratio (mol %) (mol %) (h-1) anisole anisole
1.0 60.0 60.0 9.5 35.0 65.0
3.0 23.0 69.0 11.0 32.0 68.0
5.0 14.5 72.5 11.5 25.0 75.0
10.0 7.5 75.0 11.9 24.0 76.0
a Reaction conditions: anisole/solvent or water ) 1:5 (wt/wt), catalyst

A (TS-1/33) ) 20 wt % with respect to anisole; temperature ) 80 °C; time

) 6 h; H2O2 was added in a lot under vigorous stirring.

Figure 1. Hydroxylation of anisole. The effect of reaction time on the

conversion and selectivity: anisole/H2O2 ) 5:1 (mol/mol), H2O2 was added
in a lot; water/toluene ) 5 (wt/wt), catalyst TS-1 (sample A, Si/Ti ) 33)
) 20 wt % with respect to toluene; temperature ) 80 °C; time ) 8 h.

Table 2. Effect of Reaction Temperature in the Hydroxylation of

Anisolea
product distribution, mol %
anisole H2O2
temp. conv. effi. TOF o-hydroxy- p-hydroxy-
(°C) (mol %) (mol %) (h-1) anisole anisole
30 8.0 40.0 6.3 45.0 55.0
40 11.3 56.5 9.0 34.8 65.2
60 13.3 66.5 10.6 32.0 68.0
80 14.5 72.5 11.5 25.0 75.0
100 12.0 60.0 9.5 30.0 70.0 Figure 2. Effect of dilution in the hydroxylation of anisole: anisole/H2O2
) 5:1 (mol/mol), H2O2 was added in a lot; water/toluene ) 5 (wt/wt),
aReaction conditions: anisole/solvent or water ) 1:5 (wt/wt), catalyst catalyst TS-1 (sample A, Si/Ti ) 33) ) 20 wt % with respect to toluene;
A (TS-1/33) ) 20 wt % with respect to anisole, anisole/H2O2 ) 5:1 (mol/ temperature ) 80 °C; time ) 8 h.
mol); time ) 6 h; H2O2 was added in a lot under vigorous stirring.

Table 3. Effect of Catalyst Concentration in the Hydroxylation of Table 4 depicts the effect of anisole/H2O2 molar ratio. With
Anisolea an increase in the anisole/H2O2 mole ratio from 1 to 5, there is
product distribution, mol % a marginal increase in H2O2 efficiency and TOF. This is because
anisole H2O2 the side reactions as well as the self-decomposition of H2O2
temp. conv. effi. TOF o-hydroxy- p-hydroxy- are minimized at higher anisole/H2O2 molar ratios. Another
(°C) (mol %) (mol %) (h-1) anisole anisole prominent feature is that the selectivity for the p-isomer also
30 8.0 40.0 6.3 45.0 55.0 increases with the increase in the anisole/H2O2 molar ratio. It
40 11.3 56.5 9.0 34.8 65.2 could well be that, at low anisole/H2O2 molar ratios (the
60 13.3 66.5 10.6 32.0 68.0 presence of a relatively larger amount of H2O2), the relative
80 14.5 72.5 11.5 25.0 75.0
concentration of the external surface-active species compared
100 12.0 60.0 9.5 30.0 70.0
to that by the active species situated inside the pore is relatively
a Reaction conditions: anisole/solvent or water ) 1:5, 9 wt/wt), anisole/
increased, as one would expect from concentration-dependent
H2O2 ) 5:1 (mol/mol); temperature ) 80 °C; time ) 6 h; H2O2 was added
in a lot under vigorous stirring.
phenomenon.
The influence of the dilution on the hydroxylation of anisole
facile compared to the selective catalytic hydroxylation to under solvent-free triphase conditions over the TS-1/ H2O2
produce hydroxyanisoles. Hence, a decrease was observed in system is shown in Figure 2. The optimum condition is reached
the conversion of the organic substrate because of the nonselec- when the H2O/anisole (wt/wt) ratio is 5. This is reflected by
tive H2O2 decomposition. Table 3 reports the influence of the H2O2 efficiency. It is likely that, at this particular ratio of
catalyst concentration, where it was observed that maximum H2O/anisole (wt/wt), the transport of the organic mass to the
H2O2 efficiency could be obtained when the catalyst concentra- catalyst surface is facilitated through microdroplet formation.13,14
tion is ∼15-20 wt % with respect to the substrate. As the Beyond this value, there is no further improvement of the
catalyst amount is increased, the number of active titanium reaction.
moieties available for the reaction increases and, hence, the Table 5 exhibits the effect of different TS-1 catalysts with
conversion also increases, as expected. However, when TOF different Ti-contents (catalysts A-C). With decreasing Ti-
values are compared, it was observed that there is a gradual content, there is a progressive decrease in conversion (due to
decrease in TOF with increasing catalyst concentration. This the lower concentration of active sites) accompanied by a
may be due to the agglomeration of catalyst at higher catalyst gradual increase in para-selectivity. However, there is a definite
concentrations. increase in TOF with decreasing Ti-content (increasing Si/Ti

Table 5. Effect of Different Catalysts in the Hydroxylation of
Anisolea
product distribution, mol %
anisole H2O2
catalyst conv. effi. TOF o-hydroxy- p-hydroxy-
(Si/Ti) (mol %) (mol %) (h-1) anisole anisole
A (33) 14.5 72.5 11.5 25 75
B (58) 12.0 60.0 16.5 23 77
C (80) 10.0 50.0 18.8 20 80
a Reaction conditions: anisole/water ) 1:5 (wt/wt), catalyst ) 20 wt %
with respect to anisole; temperature ) 80 °C; time ) 6 h; H2O2 was added
in a lot under vigorous stirring.
molar ratio) of the TS-1 samples used as catalysts, probably
due to better site isolation in the catalyst with lower Ti-contents.
The observed fact that there is significantly higher substrate
conversion, H2O2 efficiency, and TOF under triphase conditions
vis-à-vis that under biphase conditions in the presence of an
organic solvent is further supported by the competitive adsorp-
tion experiment followed by desorption. First, for the adsorption
experiments, two sets of adsorption experiments were conducted.
In the first one, the catalyst was slurried with water and anisole,
maintaining exactly the same composition as was used for the
reaction, except hydrogen peroxide, at the reaction temperature
(80 °C) for 6 h. In the second one, water was replaced by
acetone, keeping all other conditions same. For the desorption
experiments, 5 g of catalyst, obtained from the adsorption
experiment, was first dried at 80 °C in flowing air and then it
was loaded in a tubular downflow reactor and flushed with dry
nitrogen (by gradually increasing the temperature up to 250 °C
at the heating rate of 10 °C min-1). The desorbed material was
collected in a liquid nitrogen trap, weighed, and analyzed by
gas chromatography using FID for the acetone-anisole mixture
and a thermal conductivity detector (TCD) for the water-anisole
mixture. It was observed that ca. 90% of the total desorbed
material was acetone in the case of the acetone-anisole mixture.
However, ca. 93% of the desorbed material was anisole in the
case of the anisole-water mixture, which was also confirmed
by weighing the anisole and water layers, giving 90% anisole
and 10% water. This is in accordance with similar experiments
reported in our earlier paper on benzene hydroxylation.8 On the
basis of the above observations, it can be stated that, under
triphase conditions, the reactions take place inside the pores
predominantly, whereas under biphase conditions, the surface
reaction plays the significant role.
An important observation was made when the competitive
reaction was carried out between cyclohexane and anisole both
in biphase and triphase. Table 6 depicts the competitive reaction
between anisole and cyclohexane. The results show that, under
triphase, it is the anisole that is preferentially oxidized in the
presence of cyclohexane. When the competitive reaction was
carried out in biphase using acetone as solvent, both the anisole
and the cyclohexane were oxidized with ca. 40% H2O2 ef-
ficiency. No reaction of cyclohexane alone was observed under
triphase. However, when acetone was used as a solvent,
considerable conversion of cyclohexane to cyclohexanol/cyclo-
hexanone was observed. The triphasic hydroxylation of anisole
with TS-1/H2O2 was also carried out under inert atmosphere
(both in static nitrogen and under nitrogen blanket). There was
no effect of inert atmosphere on both conversion or product
distribution. The preferential reaction of anisole in the presence
of cyclohexane and the reactions under inert atmosphere
indicates that hydroxylation of anisole under the present triphase
condition is, at least, not going through the radical intermediate.
Ind. Eng. Chem. Res., Vol. 46, No. 25, 2007 8661
This point is discussed in more detail in the following section
dealing with the hydroxylation of toluene.
3.2.2. Toluene Hydroxylation. Direct hydroxylation of
toluene is an attractive route for the preparation of cresols. As
mentioned above (Scheme 2), there are two types of oxidation
sites available in toluene, namely, the primary carbon atom of
the side-chain methyl group and the aromatic ring. As in the
case of anisole, toluene hydroxylation under SLL triphase
conditions gives more p-cresol along with significantly higher
H2O2 effeciency toward cresol formation and, consequently,
higher conversion of toluene compared to that obtained in the
presence of organic solvents under biphase (Table 7). There
was no side-chain oxidation observed (Scheme 2). Here also,
all further studies on toluene hydroxylation were carried out
under triphase conditions using water as reaction medium.
Additionally, under triphase conditions, the reaction takes place
almost without an induction period where the reaction is
reasonably fast from the very beginning, while under biphase
conditions, it requires a relatively long induction period
Figure 3 depicts the influence of stirring speed on the catalytic
hydroxylation of toluene in triphase. The conversion as well as
para-selectivity increased with an increase in stirring speed
before it leveled off at ca. 400 rpm. This is in line with our
earlier report in the case of benzene hydroxylation.8 All other
experiments were carried out under vigorous stirring. As
expected, with increasing stirring speed, the diffusion of the
reactant from the bulk to the catalyst surface will also increase,
resulting in increased conversion. Interestingly, the selectivity
for p-cresol also increased with stirring speed along with
conversion. The increase in p-cresol formation was at the cost
of o-cresol formation, indicating that the enhanced stirring speed
favors conversion and p-isomer formation. This may be because,
with an increase in stirring rate (and, therefore, increased
transport of the reactant to the catalyst and its diffusion inside
the pore), the reaction occurs preferentially inside the TS-1
channels, thereby resulting in higher conversion and para-
selectivity. In Figure 4, the progress of the reaction is plotted
as a function of reaction time, showing that the reaction was
reasonably fast from the beginning and both the o- and p- cresol
formations took place simultaneously. The increase in conver-
sion and H2O2 efficiency with time was associated with a pro-
gressive increase in para-selectivity. Maximum H2O2 efficiency
and para-selectivity were observed at 6 h before leveling off.
Table 8 presents the results obtained as a function of reaction
temperature in the formation of cresols from toluene using the
TS-1/H2O2 system under triphase conditions. At room temper-
ature, both the H2O2 efficiency and p-cresol selectivity were
very low. The selectivity for p-cresol and the H2O2 efficiency
increased with the increase in temperature, as expected. At 80
°C, maximum H2O2 efficiency and p-cresol selectivity were
obtained. Table 9 reports the effect of catalyst concentration
on the hydroxylation of toluene. An increase in catalyst
concentration with respect to substrate or total reaction mass
resulted in an increase in H2O2 efficiency and p-cresol selectivity
up to 20 wt % catalyst concentration with respect to toluene.
This is expected because the increase in catalyst concentration
was associated with the increase in utilization of H2O2. At 30
wt % of the catalyst with respect to toluene, though the H2O2
efficiency increased marginally, the p-cresol selectivity de-
creased. The active species present on the surface might play
an increased contributory role with the increase in optimum
catalyst concentration. However, the TOF increased with
decreasing catalyst concentration, as was observed and explained
in the case of anisole hydroxylation mentioned above.
8662 Ind. Eng. Chem. Res., Vol. 46, No. 25, 2007

Table 6. Competitive Reactions between Anisole and Cyclohexanea

product distribution, mol %
substrate solvent conv. (mol %) H2O2 effi. (mol %) TOF (h-1) 2-OH anisole 4-OH anisole cyol cyone others
anisole + cyclohexane water 12.0 60 9.5 30 70
anisole + cyclohexane acetone 8.0 40 6.3 15 30 15 35 10
cyclohexane water 0.0 0.0 0.0 0 0 0 0 0
cyclohexane acetone 8.0 40.0 6.3 18 66 16
a Reaction conditions: anisole/H O ) 1:5 (wt/wt), cyclohexane/H O ) 1:5, catalyst A ) 20 wt % with respect to both anisole and cyclohexane, substrate/
2 2
H2O2 ) 5.0 (mol/mol); temperature ) 80 °C; time ) 6 h; H2O2 was added in a lot under vigorous stirring.

Table 7. Effect of Solvent/Dispersion in the Hydroxylation of

Toluenea
product selectivity
(mol %)
toluene H2O2
solvent/dispersion conv. effi. TOF
medium (mol %) (mol %) (h-1) o-cresol p-cresol
acetone 1.0 5.0 0.7 75.0 25.0
methanol 2.0 10.0 1.4 61.5 28.5
t-BuOH 2.5 12.5 1.8 12.4 87.6
water 8.3 41.5 5.8 34.0 66.0
a Reaction conditions: toluene/H O or solvent ) 1:5 (wt/wt %), catalyst
2
A ) 20 wt % with respect to toluene, substrate/H2O2 ) 5.0 (mol/mol);
temperature ) 80 °C; time ) 8 h; toluene/H2O2 ) 5:1 (mol/mol); H2O2
was added in one lot.

Figure 4. Effect of reaction time in the hydroxylation of toluene (reaction

conditions are the same as those mentioned in the legend for Figure 3).

Table 8. Effect of Temperature in the Hydroxylation of Toluenea

product selectivity (mol %)
tolune H2O2
temp. conv. effi. TOF
(°C) (mol %) (mol %) (h-1) o-cresol p-cresol
30 2.0 10.0 1.4 45 55
50 3.0 15.0 2.1 38 62
70 5.0 25.0 3.5 34 66
80 8.3 41.5 5.8 34 66
a Reaction conditions: toluene/water ) 1:5 (wt/wt), toluene/H O ) 5:1
2 2
(mol/mol), H2O2 was added in a lot; water/toluene ) 5 (wt/wt), catalyst
TS-1 (sample A, Si/Ti ) 33) ) 20 wt % with respect to toluene; time )
8 h.
Figure 3. 3. Effect of stirring speed in the hydroxylation of toluene.
Reaction conditions: toluene/H2O or solvent ) 1:5 (wt/wt %), catalyst A Table 9. Effect of Catalyst Concentration in the Hydroxylation of
) 20 wt % with respect to toluene; temperature ) 80 °C; time ) 8 h; Toluenea
toluene/H2O2 ) 5:1 (mol/mol), H2O2 was added in one lot. product selectivity (mol %)

Figure 5 depicts the effect of the toluene-to-H2O2 molar ratio catalyst H2O2
conc. conv. effi. TOF
on the triphase catalytic hydroxylation of toluene. With an (wt %) (wt %) (mol %) (h-1) o-cresol p-cresol
increase in the toluene-to-H2O2 molar ratio, there was a
5 5.0 25.0 14.0 34 66
progressive increase in H2O2 efficiency as well as para- 10 6.0 30.0 8.4 35 65
selectivity. At a lower toluene-to-H2O2 molar ratio, e.g., 1:1, 20 8.3 41.5 5.8 34 66
surface-active species might play a considerable role. While at 30 10.0 50.0 4.7 42 58
a high ratio of toluene to H2O2, active species inside the pores a Reaction conditions: toluene/H O ) 5:1 (mol/mol), H O was added
2 2 2 2
may be mainly contributing. Thus, at a low toluene-to-H2O2 in a lot; toluene/water ) 1:5 (wt/wt), catalyst TS-1 (sample A, Si/Ti ) 33)
molar ratio, the selectivity for p-cresol was less compared to ) 20 wt % with respect to toluene; temperature ) 80 °C; time ) 8 h.
that at a higher molar ratio. Table 10 reports the effect of dilution
on the triphasic hydroxylation of toluene. With an increase in there was a progressive increase in p-cresol selectivity and TOF,
dilution, i.e., H2O-to-toluene wt ratio, there was an increase in although there was a decrease in H2O2 efficiency. Similar
H2O2 efficiency, TOF, and p-cresol selectivity. The optimum observations were made and explained in the case of anisole
dilution level was found to be at H2O/toluene (wt/wt) ) 5. hydroxylation mentioned above (Section 3.2.1).
Beyond this value, there is no improvement either in H2O2 The result of competitive reactions between toluene and
efficiency or in p-cresol selectivity. cyclohexane in the presence of the TS-1/ H2O2 system under
In Table 11, the results obtained over different TS-1 catalysts triphase showed that there was no reaction of cyclohexane in
(with different Ti-contents) for the catalytic hydroxylation of the presence of toluene under triphase. Only toluene was
toluene under triphase are presented. With increasing Si/Ti ratio, preferentially converted to o- and p-cresols. However, the H2O2
 Ind. Eng. Chem. Res., Vol. 46, No. 25, 2007 8663

Table 12. Oxidation of Benzyl Chloride (4), in Biphase (Solvent )

Acetonitrile) and Solvent-free Triphase Conditionsa
phase
biphase triphase
substrate/H2O2 mol ratio 1 1 2 3
conversion (mol % of theo. max) 3.0 38.0 53.0 54.0
H2O2 efficiency (mol %) 4.0 43.0 58.0 59.0
reaction time (h) 12.0 6.0 6.0 6.0
TOF (h-1) 0.3 5.8 7.9 8.0
Products (mol %)
benzyl alcohol 80.0
benzaldehyde, 4a 15.0 31.5 20.0 17.5
benzoic acid, 4b 5.0 7.5 1.5 1.5
o-hydroxybenzyl chloride, 4c 6.0 7.5 9.5
p-hydroxybenzyl chloride,4d 49.5 63.0 64.5
o-hydroxybenzaldehyde, 4e 2.0 2.5 3.0
p- hydroxybenzaldehyde, 4f 3.5 4.5 4.5
side-chain oxidation (4a + 4b) 41.0 23.5 20.5
ring hydroxylation (4c + 4d + 4e + 4f) 59.0 76.5 80.5
Figure 5. 5. Effect of toluene-to-H2O2 mole ratio in the hydroxylation of
toluene. Reaction conditions: toluene/H2O or solvent ) 1:5 (wt/wt %), Isomer Distribution, %
ortho-hydroxy products 14 12.6 14.9
catalyst A ) 20 wt % with respect to toluene; temperature ) 80 °C; time
para-hydroxy products 85.8 87.4 85.1
) 8 h.
a Reaction conditions: substrate/solvent or water ) (wt/wt) 1: 5, catalyst
Table 10. Effect of Dilution in the Hydroxylation of Toluenea (TS-1/33) ) 20 wt % with respect to substrate, substrate/H2O2 ) 5.0 (mol/
product selectivity (mol %) mol); temperature ) 80 °C; H2O2 was added in a lot under vigorous stirring.

H2O2
H2O/toluene conv. effi. TOF toluene conversion and lower selectivity toward p-cresol. From
(wt/wt) (wt %) (mol %) (h-1) o-cresol p-cresol
this competitive experiment, the possibility of a radical inter-
1:1 3.0 15.0 2.1 44 56 mediate under the triphase conditions was ruled out. If the
3:1 8.5 42.5 6.0 40 60 radical intermediate had been involved in the reaction, then it
5:1 8.3 41.5 5.8 34 66
10:1 10.0 50.0 7.0 39 61 is more likely that cyclohexane would undergo oxidation and
a Reaction conditions: toluene/H O ) 5:1 (mol/mol), H O was added
not the aromatic compound, because, in the later case, the radical
2 2 2 2
in a lot; toluene/water ) 1: 5 (wt/wt), catalyst TS-1 (sample A, Si/Ti )
will be formed on the aromatic ring, which is energetically
33) ) 20 wt % with respect to toluene; temperature ) 80 °C; time ) 8 h. highly unfavorable. Therefore, the possibility of the involvement
of a radical intermediate may be ruled out in the triphase
conditions.
Table 11. Effect of Different TS-1 in the Hydroxylation of Toluenea
This was further supported when the reaction was carried out
product selectivity (mol %) under nitrogen and under flowing nitrogen. The purpose of
H2O2 carrying out the reaction under an inert atmosphere is two-
conv. effi. TOF fold: (i) to find out whether oxygen in air is taking part in the
catalyst (wt %) (mol %) (h-1) o-cresol p-cresol reaction and (ii) to understand the possible reactive intermediate
A (33) 8.3 41.5 7.7 34.0 66.0 responsible for hydroxylation under the present triphase condi-
B (58) 3.5 17.5 5.6 27.4 72.6 tions. If molecular oxygen is responsible for the reaction, the
C (80) 2.0 10.0 2.2 29.9 74.1
nitrogen flow as well as the reaction under the nitrogen blanket
a Reaction conditions: toluene/H O ) 5:1 (mol/mol), toluene/water )
2 2 will suppress the reaction. Further, if the titanium-peroxo
1:5 (wt/wt), H2O2 was added in a lot; water/toluene ) 5 (wt/wt), catalyst species is responsible for hydroxylation, then the flow of
20 wt % with respect to toluene; temp. ) 80 °C; time ) 8 h.
nitrogen will break the species and so will suppress the reaction.
Scheme 3: Oxidation of Cyclohexane If there is no such effect, the reaction may well go through the
titanium-hydroperoxo species rather than Ti-peroxo species.
The results obtained under inert atmosphere show that there
was no change (within the experimental limit) either in
conversion or in selectivity. Therefore, considering the competi-
tive reaction between toluene and cyclohexane and the observa-
tion obtained under inert atmosphere, the titanium-peroxo
efficiency and para-selectivity were considerably lower in the species as the reaction intermediate can be ruled out. Therefore,
presence of cyclohexane. The reaction of cyclohexane over the the possible reactive species responsible for the hydroxylation
TS-1/H2O2 system in the presence of acetone gave mainly of anisole as well as toluene under triphase could be the Ti-
cyclohexanol and cyclohexanone along with some unidentified hydroxyperoxy species.5
heavy products (Scheme 3). However, there was no reaction of 3.2.3. Benzylchloride Hydroxylation/Oxidation. In Table
cyclohexane in the triphase in the presence of water, as 12, the results obtained in the direct hydroxylation of benzyl-
mentioned above in the section on anisole hydroxylation. Since chloride under triphase (solvent-free aqueous medium) and
both the cyclohexane and the toluene get adsorbed inside the biphase (in the presence of organic cosolvent) reaction condi-
TS-1 channels and cyclohexane did not get converted, it tions are presented (see Scheme 4). Very interesting results were
prevented, to some extent, the adsorption of toluene. Therefore, obtained in the case of benzyl chloride where an electron-
in the presence of cyclohexane, the surface reactions contributed withdrawing group (-CH2Cl), unlike electron-donating groups
considerably to the product distribution, resulting in the lower (-CH3 or -OH), is present. Under biphase conditions, only
8664 Ind. Eng. Chem. Res., Vol. 46, No. 25, 2007
Scheme 4: Hydroxylation/Oxidation of Benzyl Chloride
ca. 3% conversion of benzylchloride could be obtained as
compared to 38-54% under triphase conditions. Further, the
product distribution under biphase and triphase conditions was
completely different. Under biphase, no ring hydroxylation took
place and the only products obtained were due to hydrolysis of
the C-Cl bond, giving benzyl alcohol (80%), benzaldehyde
(15%), and benzoic acid (5%). No ring hydroxylation took place
in the presence of organic solvent acetone. However, under
triphase, a significant amount of ring hydroxylation (80%) was
obtained along with side-chain oxidation giving benzaldehyde
(18%) and benzoic acid (2%) where no benzyl alcohol was
obtained, even in the beginning of the reaction. The complete
absence of benzyl alcohol even at the initial stage of the reaction
clearly indicated the oxidation of the side chain followed by
HCl removal, directly giving benzaldehyde and a small amount
of benzoic acid. This is in complete contrast with the product
distribution obtained in biphase conditions using organic solvent,
where the hydrolysis of the -CH2Cl group to -CH2OH,
followed by its oxidation to benzaldehyde, was the main
reaction.
4. Conclusions
In summary, it can be stated that the solvent-free triphase
catalytic oxidation of substituted benzenes like anisole, toluene,
and benzylchloride over the TS-1/H2O2 system leads to an
enhancement in the reaction rate as well as the para-selectivity.
Since TS-1 is relatively hydrophobic in nature, the reactants
compete favorably with water for diffusion inside the zeolite
channels under triphase, thereby resulting in greater conversion
and better shape selectivity. Although, in the case of anisole
and toluene, the products are the same in both biphase and
triphase conditions, the product isomer distribution was quite
different where o- and p-isomers were the major products under
biphase and triphase conditions, respectively. However, in the
case of benzyl chloride, the products formed under biphase
(using organic solvent) and triphase (no organic solvent, only
water was used as reaction medium) are quite different because
of the different reaction paths operating in the presence (biphase)
and absence (triphase) of organic solvent. Under biphase (using
acetone as solvent), no ring hydroxylation could be achieved
and a very minor reaction of hydrolysis of benzylchloride to
benzylalcohol, followed by its oxidation to benzaldehyde (4%
H2O2 efficiency), took place. However, under triphase with
water as reaction medium, significant conversion (43-59%
H2O2 efficiency) was achieved with ca. 80 mol % selectivity
for ring-hydroxylation products among total products formed,
and the remaining 20 mol % selectivity was for the products
formed by the oxidation of side chains to benzaldehyde and
benzoic acid. No benzyl alcohol was formed, even at low
conversion and at initial stages of the reaction.
Apart from these activity and selectivity advantages, the
present triphase method offers a distinct advantage in easier
product recovery due to phase separation of the organic layer
containing unconverted reactant and products and the aqueous
layer consisting of water and unconverted H2O2, if any. This is
also a major advantage from energy-saving and green-chemical
points of views. The competitive reaction between cyclohexane
and anisole, both under biphase and triphase, and also the
reactions under inert atmosphere suggest the ionic mechanism
of the reaction rather than the radical one.
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ReceiVed for reView January 14, 2007
ReVised manuscript receiVed October 12, 2007
Accepted October 12, 2007
IE070088Q