Ultrasonics Sonochemistry 16 (2009) 308–311

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Ultrasonics Sonochemistry
journal homepage: www.elsevier.com/locate/ultsonch

Short Communication

Ultrasound assisted regioselective sulfonation of aromatic compounds

with sulfuric acid
Ziyauddin S. Qureshi, Krishna M. Deshmukh, Sachin R. Jagtap, Nitin S. Nandurkar, Bhalchandra M. Bhanage *
Department of Chemistry, Institute of Chemical Technology, University of Mumbai, N. Parekh Marg, Matunga, Mumbai 400 019, India

a r t i c l e i n f o a b s t r a c t

Article history: A simple and convenient methodology for selective sulfonation of aromatic compounds using sulfuric
Received 9 June 2008 acid under sonication is described. The present methodology shows a considerable enhancement in
Received in revised form 4 October 2008 the reaction rate along with improved selectivity compared with the reactions performed under silent
Accepted 8 October 2008
conditions. The effect of various parameters such as agitation speed, sulfuric acid concentration, and tem-
Available online 17 October 2008
perature on reaction system have been investigated and are explained on the basis of ultrasonically gen-
erated cavitational effects.
PACS:
*43.35. c Ó 2008 Elsevier B.V. All rights reserved.
81.20.Ka

Keywords:
Ultrasound
Sulfonation
Aromatic hydrocarbon
Sulfuric acid

1. Introduction
The sulfonation of aromatic compounds is one of the important
reactions in organic transformations and many aromatic hydrocar-
bons have been sulfonated [1]. Several methods have been reported
in the literature for the sulfonation of aromatic compounds such as,
sulfonation of aromatic compounds with concentrated sulfuric acid
[2], trifluoro acetic acid–sulfuric acid [3], sulfur trioxide in dichloro-
methane [4], sulfonation of Grignard and lithium reagents [5],
nucleophilic aromatic substitution with sodium sulfite [6], and sul-
fonation with sulfur tri oxide–dioxane complex [7]. Recently silica
supported sulfuric acid sulfonation of aromatic compounds have
been reported [8]. But the methods employed so far for the sulfona-
tion of aromatic compounds have several disadvantageous such as
longer reaction time, high temperature, higher concentration and
lower yield.
In recent years the use of ultrasound in organic transformations
is well known as it can enhance the rate, yield and selectivity of the
reactions. It can also facilitate reactions at ambient conditions
eliminating requirement of drastic conditions such as temperature,
pressure or concentrations [9]. The driving force for the ultrasound
developments in organic synthesis has many facets, The increasing
demand for environmentally clean technologies that can mini-
* Corresponding author. Tel.: +91 22 24145616; fax: +91 22 24145614.
E-mail address: bhalchandra_bhanage@yahoo.com (B.M. Bhanage).
mizes the production of waste at source. Thus ultrasound may offer
cleaner reactions by improving product yield, selectivity, enhance-
ment in product recovery and purification processes. Sonication
also allows the use of non-activated and crude reagents as well
as an aqueous solvent system; therefore it is environment friendly.
Ultrasound is widely used for improving the traditional reactions
that require expensive reagents, strongly acidic conditions, longer
reaction time, high temperatures, unsatisfactory yields and incom-
patibility with other functional groups. Although the use of ultra-
sound has been wide spread, the specific reasons for the rate
enhancement in the presence of ultrasound are not known. In lit-
erature various mechanisms such as single electron transfer, stress
created due to implosion of cavities, an increase in the mass trans-
fer coefficients due to increase in the contact surface area [10], high
temperature and pressures reached during cavitational collapse
are held responsible for the spectacular effects observed as a result
of ultrasound. It has also been speculated that the free radicals pro-
duced during cavitation initiate many reactions in the bulk, thus
enhancing the rate of reactions [11]. The presence of a supercritical
region at the interface of the solution and cavity is also supposed to
enhance the rate of some reactions.
In continuation of our special interest in ultrasound assisted or-
ganic transformations [12], we herein report for the first time sul-
fonation of aromatic compounds using sulfuric acid as sulfonating
agent under solvent free conditions by sonication. The present
methodology shows a considerable enhancement in the reaction

1350-4177/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.ultsonch.2008.10.001
 Z.S. Qureshi et al. / Ultrasonics Sonochemistry 16 (2009) 308–311
rate along with improved selectivity compared with reactions per-
formed under silent conditions.
2. Experimental
Fig. 1 shows a typical experimental setup used for ultrasound-
mediated reactions. Various materials and equipment used in the
experimental methodology have been described in the following
sections.
2.1. General
All the chemicals were obtained from commercial source and
used as it is. The progress of the reaction was monitored using
HPLC [Jasco LC-900 series with uv/vis detector (Jasco-975) at
280 nm, Column (Jasco Model: Finebak SIL C8–10), Acetonitrile:
water (60:40) as a mobile phase and 0.2% ammonium acetate buf-
fer solution]. Mechanical agitator (six-blade, pitched-blade made
up of glass) with automated speed control was used. All products
were confirmed by LC using authentic standards and also by their
physical constant reported in the literature [13].
2.2. Typical procedure for sonochemical sulfonation
In a typical reaction, a 100 ml round bottom flask equipped with
mechanical stirrer was placed at the centre of ultrasonic bath hav-
ing maximum cavitations. To it toluene (0.1 mol) was added and
afterwards concentrated sulfuric acid (98 wt%, 0.12 mol) was
added drop wise. The reaction mixture was then sonicated at room
temperature (25 oC) up to desired time. The ultrasonic bath used
had a frequency of 33 kHz and electric power rating of 100 W. After
completion the reaction mixture was subjected to HPLC analysis
and the experimental error is of ±5%.
3. Results and discussion
The sulfonation of aromatic compounds was performed using
sulfuric acid in presence of ultrasound and the results were com-
pared with those obtained without ultrasound. The typical reaction
scheme is shown in Scheme 1.
Two sets of experiments have been carried out: (1) experiments
were carried out under silent conditions with mechanical agitation
and (2) same experiments were carried out under ultrasonic irradi-
ation with mechanical agitation. Using this comparison the
Fig. 1. Experimental setup for sulfonation of aromatic compounds under
sonication.
309
SO3H
)))))
R + Conc. H2SO4 R
25 ºC
R = H, CH3, OCH3, -X, Ar etc
Scheme 1. Sulfonation of aromatic compounds under sonication.
efficiency of using ultrasound over a conventional system can be
quantified. The methodology was applied to various aromatic com-
pounds and the results are summarized in Table 1. It has been ob-
served that the sulfonation of toluene under silent condition
required 24 h for 70% conversion and the selectivity towards p-tol-
uene sulfonic acid was up to 90% (Table 1 entry 1). However, when
the same reaction was performed under sonication the reaction
showed a significant rate enhancement and the reaction got com-
pleted within 45 min providing 76% conversion and the selectivity
towards p-toluene sulfonic acid was improved up to 100% (Table 1
entry 2). The protocol was further extended to various activated
aromatic compounds such as o-xylene, m-xylene, p-xylene and ani-
sole and all were found to provide good conversion and selectivity.
The system was further extended to deactivated aromatic com-
pound like chloro benzene and was also found to provide similar
results. The probable reason for the significant rate enhancement
could be due to the well-discussed cavitation effect observed under
sonication. The cavitation effect, which plays an important role of
enhancing the interaction between the aromatic compound and
sulfuric acid thus providing higher conversion, which is otherwise
difficult to achieve under silent condition.
The effects of various parameters such as agitation speed, sulfu-
ric acid concentration, and temperature on reaction system have
been investigated and are discussed as follows.
3.1. Effect of agitation speed
The agitation speed plays an important role under sonication
and showed interesting behavior. Here again the two sets of exper-
iments were carried out to study the effects of agitation. (1) Exper-
iments without agitation (2) experiments with agitation speed in
the range of 200–800 rpm (Fig 2). It was observed that in the ab-
sence of agitation under sonication, the conversion of toluene
was 66% and did not proceed further. The reaction with mild agita-
tion speed of 200–400 rpm shows increase conversion to 76%, indi-
cating that there is a role played both by the microlevel mass
transfer caused due to the turbulence created by ultrasound and
macrolevel mass transfer caused by agitator. However the major
role is played due to the turbulence created by ultrasound. How-
ever when the agitation speed was further increased to 600 and
800 rpm conversion of toluene was lowered considerably (below
50%) and the probable reason may be that, higher agitation speed
might be affecting the microlevel mass transfer generated by ultra-
sound hindering the formation of active SO3H radicals responsible
for sulfonation. This indicates that ultrasonic irradiation and agita-
tion in combination does give synergistic effects up to certain agi-
tation speed with major role played by ultrasound [12b].
3.2. Effect of sulfuric acid concentration
The effects of sulfuric acid concentration on the reaction system
have been investigated and the results are presented in Table 2.
Sulfonation of toluene with different mole ratio of concentrated
sulfuric acid (0.8–1.4 mole) was carried out. It was observed that
with increase in the concentration of sulfuric acid there is a consid-
erable increase in the conversion of toluene toward p-toluene
310 Z.S. Qureshi et al. / Ultrasonics Sonochemistry 16 (2009) 308–311

Table 1
Sulfonation of aromatic compounds with concentrated H2SO4 with and without ultrasound.

Entry Substrate Condition Time Conversion (%) Selectivity (%) Product Mp (oC)
1 Toluene Silent 24 h 70 90 Toluene-4-sulfonic acid 99–102
2 Toluene ))))) 45 min 76 100 Toluene-4-sulfonic acid 99–102
3 Benzene Silent 5h 13 80 Benzenesulfonic acid 45–47
4 Benzene ))))) 45 min 28 100 Benzenesulfonic acid 45–47
5 Naphthalene Silent 5h 11 87 Naphthalene-1-sulfonic acid 79–81
6 Naphthalene ))))) 45 min 66 100 Naphthalene-1-sulfonic acid 79–81
7 o-Xylene Silent 5h 37 90 3,4-Dimethyl-benzenesulfonic acid 81–83
8 o-Xylene ))))) 45 min 70 100 3,4-Dimethyl-benzenesulfonic acid 81–83
9 m-Xylene Silent 5h 10 90 2,4-Dimethyl-benzenesulfonic acid 61–63
10 m-Xylene ))))) 45 min 82 100 2,4-Dimethyl-benzenesulfonic acid 61–63
11 p-Xylene Silent 5h 70 90 2,5-Dimethyl-benzenesulfonic acid 89–91
12 p-Xylene ))))) 45 min 76 100 2,5-Dimethyl-benzenesulfonic acid 89–91
13 Anisole Silent 5h 60 84 4-Methoxy-benzenesulfonic acid 88–90
14 Anisole ))))) 45 min 80 100 4-Methoxy-benzenesulfonic acid 88–90
15 Chloro benzene Silent 5h 2 70 4-Chloro-benzenesulfonic acid 85–87
16 Chloro benzene ))))) 45 min 10 100 4-Chloro-benzenesulfonic acid 85–87

Reaction condition: substrate (0.1 mol); concentrated H2SO4 (98 wt%) (0.12 mol); agitation speed 200 rpm; temperature 25–30 oC; conversion is based on HPLC analysis.

Table 3
Effect of agitation
Effect of temperature under sonication.
Conversion/ product formation

100
Entry Temperature (°C) Time (min) Conversion (%)
80
1 25–30 45 76
2 50–55 45 78
60
3 80–85 45 43
(%)

40 Reaction condition: toluene (0.1 mol); concentrated H2SO4 (98 wt%) (0.12 mol);
agitation speed 200 rpm; time 45 min. Conversion is based on HPLC analysis.
20

0
0 200 400 600 800 1000 cavitational effect generated by ultrasound gets affected leading to
Agitation speed (rpm) lower conversion.

Fig. 2. Effect of agitation under sonication. Reaction condition: Toluene (0.1 mol);
concentrated H2SO4 (98 wt%) (0.12 mol); temperature 25–30 oC; time 45 min. 4. Conclusion
Conversion is based on HPLC analysis.
In conclusion, this paper reports an efficient protocol for regio-
selective sulfonation of aromatic compound under solvent free
conditions using ultrasound as promoter. The present methodol-
Table 2
Effect of sulfuric acid concentration under sonication ogy shows a considerable enhancement in the reaction rate along
with improved selectivity, when compared with the similar reac-
Entry Toluene:H2SO4 Time (min) Conversion (%)
tions performed under silent conditions. The effect of various
1 1:0.8 45 44 parameters such as agitation speed, sulfuric acid concentration,
2 1:1 45 49
and temperature on the reaction system was investigated and
3 1:1.2 45 76
4 1:1.4 45 79 shows interesting behavior.

Reaction condition: toluene (0.1 mol); concentrated H2SO4 (98 wt%) moles of sul-
furic acid to 1.25, 1, 0.83, 0.71, 0.62, agitation speed 200 rpm; temperature 25– References
30 °C; Conversion is based on HPLC analysis.
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