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2009 Ultrasound Assisted Regioselect PDF
2009 Ultrasound Assisted Regioselect PDF
Ultrasonics Sonochemistry
journal homepage: www.elsevier.com/locate/ultsonch
Short Communication
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 mizes the production of waste at source. Thus ultrasound may offer
cleaner reactions by improving product yield, selectivity, enhance-
The sulfonation of aromatic compounds is one of the important ment in product recovery and purification processes. Sonication
reactions in organic transformations and many aromatic hydrocar- also allows the use of non-activated and crude reagents as well
bons have been sulfonated [1]. Several methods have been reported as an aqueous solvent system; therefore it is environment friendly.
in the literature for the sulfonation of aromatic compounds such as, Ultrasound is widely used for improving the traditional reactions
sulfonation of aromatic compounds with concentrated sulfuric acid that require expensive reagents, strongly acidic conditions, longer
[2], trifluoro acetic acid–sulfuric acid [3], sulfur trioxide in dichloro- reaction time, high temperatures, unsatisfactory yields and incom-
methane [4], sulfonation of Grignard and lithium reagents [5], patibility with other functional groups. Although the use of ultra-
nucleophilic aromatic substitution with sodium sulfite [6], and sul- sound has been wide spread, the specific reasons for the rate
fonation with sulfur tri oxide–dioxane complex [7]. Recently silica enhancement in the presence of ultrasound are not known. In lit-
supported sulfuric acid sulfonation of aromatic compounds have erature various mechanisms such as single electron transfer, stress
been reported [8]. But the methods employed so far for the sulfona- created due to implosion of cavities, an increase in the mass trans-
tion of aromatic compounds have several disadvantageous such as fer coefficients due to increase in the contact surface area [10], high
longer reaction time, high temperature, higher concentration and temperature and pressures reached during cavitational collapse
lower yield. are held responsible for the spectacular effects observed as a result
In recent years the use of ultrasound in organic transformations of ultrasound. It has also been speculated that the free radicals pro-
is well known as it can enhance the rate, yield and selectivity of the duced during cavitation initiate many reactions in the bulk, thus
reactions. It can also facilitate reactions at ambient conditions enhancing the rate of reactions [11]. The presence of a supercritical
eliminating requirement of drastic conditions such as temperature, region at the interface of the solution and cavity is also supposed to
pressure or concentrations [9]. The driving force for the ultrasound enhance the rate of some reactions.
developments in organic synthesis has many facets, The increasing In continuation of our special interest in ultrasound assisted or-
demand for environmentally clean technologies that can mini- ganic transformations [12], we herein report for the first time sul-
fonation of aromatic compounds using sulfuric acid as sulfonating
* Corresponding author. Tel.: +91 22 24145616; fax: +91 22 24145614. agent under solvent free conditions by sonication. The present
E-mail address: bhalchandra_bhanage@yahoo.com (B.M. Bhanage). 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) 308–311 309
rate along with improved selectivity compared with reactions per- SO3H
formed under silent conditions.
)))))
R + Conc. H2SO4 R
2. Experimental 25 ºC
Fig. 1 shows a typical experimental setup used for ultrasound- R = H, CH3, OCH3, -X, Ar etc
mediated reactions. Various materials and equipment used in the
Scheme 1. Sulfonation of aromatic compounds under sonication.
experimental methodology have been described in the following
sections.
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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