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
A simple and convenient methodology for selective sulfonation of aromatic compounds using sulfuric acid under sonication is described. The present methodology shows a considerable enhancement in the reaction rate along with improved selectivity compared with the reactions performed under silent conditions. The effect of various parameters such as agitation speed, sulfuric acid concentration, and temperature on reaction system have been investigated and are explained on the basis of ultrasonically generated cavitational effects. Ó 2008 Elsevier B.V. All rights reserved.

Article history: Received 9 June 2008 Received in revised form 4 October 2008 Accepted 8 October 2008 Available online 17 October 2008 PACS: *43.35.Àc 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 hydrocarbons 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 dichloromethane [4], sulfonation of Grignard and lithium reagents [5], nucleophilic aromatic substitution with sodium sulfite [6], and sulfonation 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 sulfonation 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). 1350-4177/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.ultsonch.2008.10.001

mizes the production of waste at source. Thus ultrasound may offer cleaner reactions by improving product yield, selectivity, enhancement 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 incompatibility with other functional groups. Although the use of ultrasound has been wide spread, the specific reasons for the rate enhancement in the presence of ultrasound are not known. In literature various mechanisms such as single electron transfer, stress created due to implosion of cavities, an increase in the mass transfer 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 produced 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 organic transformations [12], we herein report for the first time sulfonation 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

-X.4 mole) was carried out. 3. Effect of agitation speed The agitation speed plays an important role under sonication and showed interesting behavior. Sulfonation of toluene with different mole ratio of concentrated sulfuric acid (0. However 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. H2SO4 ))))) 25 ºC R R = H. 1 shows a typical experimental setup used for ultrasoundmediated reactions. The system was further extended to deactivated aromatic compound like chloro benzene and was also found to provide similar results.Z. when the same reaction was performed under sonication the reaction showed a significant rate enhancement and the reaction got completed within 45 min providing 76% conversion and the selectivity towards p-toluene sulfonic acid was improved up to 100% (Table 1 entry 2). Qureshi et al. 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. OCH3.1.2. indicating 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. Ar etc Scheme 1.8–1. The cavitation effect. efficiency of using ultrasound over a conventional system can be quantified. It was observed that with increase in the concentration of sulfuric acid there is a considerable increase in the conversion of toluene toward p-toluene Fig. It has been observed that the sulfonation of toluene under silent condition required 24 h for 70% conversion and the selectivity towards p-toluene sulfonic acid was up to 90% (Table 1 entry 1). sulfuric acid concentration. The ultrasonic bath used had a frequency of 33 kHz and electric power rating of 100 W. The protocol was further extended to various activated aromatic compounds such as o-xylene.1 mol) was added and afterwards concentrated sulfuric acid (98 wt%. a 100 ml round bottom flask equipped with mechanical stirrer was placed at the centre of ultrasonic bath having maximum cavitations. Various materials and equipment used in the experimental methodology have been described in the following sections. and temperature on reaction system have been investigated and are discussed as follows. Mechanical agitator (six-blade. The progress of the reaction was monitored using HPLC [Jasco LC-900 series with uv/vis detector (Jasco-975) at 280 nm. (1) Experiments without agitation (2) experiments with agitation speed in the range of 200–800 rpm (Fig 2). 1. which plays an important role of enhancing the interaction between the aromatic compound and sulfuric acid thus providing higher conversion. The reaction mixture was then sonicated at room temperature (25 oC) up to desired time. 3. This indicates that ultrasonic irradiation and agitation in combination does give synergistic effects up to certain agitation speed with major role played by ultrasound [12b]. the conversion of toluene was 66% and did not proceed further. 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 irradiation with mechanical agitation. which is otherwise difficult to achieve under silent condition. The probable reason for the significant rate enhancement could be due to the well-discussed cavitation effect observed under sonication. However.S. It was observed that in the absence of agitation under sonication. To it toluene (0. 3. Experimental setup for sulfonation of aromatic compounds under sonication. General All the chemicals were obtained from commercial source and used as it is. Column (Jasco Model: Finebak SIL C8–10). The typical reaction scheme is shown in Scheme 1.2% ammonium acetate buffer solution]. m-xylene.1. Experimental Fig. 2. higher agitation speed might be affecting the microlevel mass transfer generated by ultrasound hindering the formation of active SO3H radicals responsible for sulfonation. . Here again the two sets of experiments were carried out to study the effects of agitation. 2. Results and discussion The sulfonation of aromatic compounds was performed using sulfuric acid in presence of ultrasound and the results were compared with those obtained without ultrasound. pitched-blade made up of glass) with automated speed control was used. Acetonitrile: water (60:40) as a mobile phase and 0. Sulfonation of aromatic compounds under sonication.2. The reaction with mild agitation speed of 200–400 rpm shows increase conversion to 76%. However the major role is played due to the turbulence created by ultrasound. Using this comparison the SO3H R + Conc. p-xylene and anisole and all were found to provide good conversion and selectivity. The effects of various parameters such as agitation speed.12 mol) was added drop wise. Typical procedure for sonochemical sulfonation In a typical reaction. The methodology was applied to various aromatic compounds and the results are summarized in Table 1. CH3. 0. 2. / Ultrasonics Sonochemistry 16 (2009) 308–311 309 rate along with improved selectivity compared with reactions performed under silent conditions. After completion the reaction mixture was subjected to HPLC analysis and the experimental error is of ±5%. All products were confirmed by LC using authentic standards and also by their physical constant reported in the literature [13].

Cerfontain. [4] T. Conclusion In conclusion. Yakovlev. Bochkareva.8 1:1 1:1.P. K. M.4-Dimethyl-benzenesulfonic acid 2. The effect of temperature was done to nullify the error of rise in temperature in the reaction.1 mol). 45 (2004) 6607. The 1:1. Conversion is based on HPLC analysis. Sheiko. [5] K. It was observed that when reaction was carried out at 25–30 oC the conversion of toluene was 76%. G. H. 1990. D.H.3. concentrated H2SO4 (98 wt%) (0.4 Time (min) 45 45 45 45 Conversion (%) 44 49 76 79 Reaction condition: toluene (0. Chem. Tetrahedron Lett. Further increase in mole ratio of sulfuric acid with respect to toluene did not have any effect on the reaction system. Agitation speed (rpm) Fig. Duanjie. Commun. Bhanage. Gary. Phase transfer catalysis and ultrasonic waves II: saponification of vegetable oils.310 Z. Chem. 4. Ruoho. Khelevin. Amin. Gilbert. agitation speed 200 rpm.S. CT. Plenum Press.P. Org. (b) T. temperature 25–30 oC. Chem. USSR 23 (1987) 1709. 1998. Falvey.W. Tucker. conversion is based on HPLC analysis. NY.A. Luche. Further increase in temperature from 50 to 55 oC did not have much effect on the conversion of toluene. Keshavazi.1 mol). A. [11] T. 0. Abdol. Effect of temperature To study the effect of temperature on sulfonation of toluene three sets of experiments were carried out in the temperature range 25–30. Effect of agitation Conversion/ product formation (%) 100 80 60 40 20 0 0 200 400 600 800 1000 Table 3 Effect of temperature under sonication. Effect of agitation under sonication.E. Qureshi et al. when compared with the similar reactions performed under silent conditions. Ultrasound Sonochem. Reaction condition: Toluene (0.H. Org.P.D.J. B. 1.S. 0. the probable reason may be that at higher temperature the . Harada. The effect of various parameters such as agitation speed.J. Ando. I. [9] (a) J. H. 60 (1995) 6563.V. [8] R.J. [2] H. [7] P. agitation speed 200 rpm. 80–85 oC under sonication and the results are presented in Table 3. New York. Tomozwaza. 61 (1996) 1530.5-Dimethyl-benzenesulfonic acid 2. Chem. The role of solvent in sonochemical reactions: the case of acetic acid. 2. 1965. Meaney. G. A.12 mol). 0. Conversion is based on HPLC analysis. T. The present methodology shows a considerable enhancement in the reaction rate along with improved selectivity. USSR (Engl. this paper reports an efficient protocol for regioselective sulfonation of aromatic compound under solvent free conditions using ultrasound as promoter. T. Synthesis (1998) 1593. K. B.J. sulfonic acid. Res. Transl.F. Corby. A. and temperature on the reaction system was investigated and shows interesting behavior. time 45 min. Perkin Trans.P.71. Fujita.83. Jean-Marc Luche. Org. Mason. temperature 25– 30 °C. concentrated H2SO4 (98 wt%) moles of sulfuric acid to 1. time 45 min. JAI Press. Chem. Chem.G. Soc. Z. Further increase in temperature from 80 to 85 oC inhibits the conversion. sulfuric acid concentration. Entezari.M. [12] (a) N.2 1:1. 50–55.N. 11 (2002) 1174.4-Dimethyl-benzenesulfonic acid 2. Bi. Table 2 Effect of sulfuric acid concentration under sonication Entry 1 2 3 4 Toluene:H2SO4 1:0. 8 (2001) 213. concentrated H2SO4 (98 wt%) (0.12 mol).G. B. agitation speed 200 rpm. / Ultrasonics Sonochemistry 16 (2009) 308–311 Table 1 Sulfonation of aromatic compounds with concentrated H2SO4 with and without ultrasound. Coombes. P. Smyth. Passet. References [1] (a) E. M. J. Synthetic Organic Sonochemistry. Chem. J. Inorg.A.M. Sulfonation and Related Reactions. Leila. [6] T. Entry 1 2 3 Temperature (°C) 25–30 50–55 80–85 Time (min) 45 45 45 Conversion (%) 76 78 43 Reaction condition: toluene (0.E.P. Wuts.2 mole ratio of toluene: H2SO4 was found to be effective. J. Org.) 25 (1989) 1346.J.4-Dimethyl-benzenesulfonic acid 2. P. [3] B.L.E.. Lawrence. Nandurkar. Conversion is based on HPLC analysis.62. temperature 25–30 oC. Kimura.J. R.S. Chem.H. Commun. concentrated H2SO4 (98 wt%) (0. 7 (2002) 326. Wiley. Z.4-Dimethyl-benzenesulfonic acid 3. 11 (2008) 73. 3. cavitational effect generated by ultrasound gets affected leading to lower conversion. Advances in Sonochemistry.1 mol). London and Greenwich. Schaasberg. Patil. Umemoto. Smith. M. Synop.12 mol).M. Hadjigeorgion. [10] M. (b) R.5-Dimethyl-benzenesulfonic acid 4-Methoxy-benzenesulfonic acid 4-Methoxy-benzenesulfonic acid 4-Chloro-benzenesulfonic acid 4-Chloro-benzenesulfonic acid Mp (oC) 99–102 99–102 45–47 45–47 79–81 79–81 81–83 81–83 61–63 61–63 89–91 89–91 88–90 88–90 85–87 85–87 Reaction condition: substrate (0.R.25. Entry 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 Substrate Toluene Toluene Benzene Benzene Naphthalene Naphthalene o-Xylene o-Xylene m-Xylene m-Xylene p-Xylene p-Xylene Anisole Anisole Chloro benzene Chloro benzene Condition Silent ))))) Silent ))))) Silent ))))) Silent ))))) Silent ))))) Silent ))))) Silent ))))) Silent ))))) Time 24 h 45 min 5h 45 min 5h 45 min 5h 45 min 5h 45 min 5h 45 min 5h 45 min 5h 45 min Conversion (%) 70 76 13 28 11 66 37 70 10 82 70 76 60 80 2 10 Selectivity (%) 90 100 80 100 87 100 90 100 90 100 90 100 84 100 70 100 Product Toluene-4-sulfonic acid Toluene-4-sulfonic acid Benzenesulfonic acid Benzenesulfonic acid Naphthalene-1-sulfonic acid Naphthalene-1-sulfonic acid 3. 2 (1985) 659. Wilson. G.1 mol). Jean-Louis Luche.

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