C
Synlett
A. R. Moosavi-Zare et al.
Letter
Table 4 The Large-Scale Sulfonation of Chlorobenzene Using [Dsim]Cl
(17) Zolfigol, M. A.; Khakyzadeh, V.; Moosavi-Zare, A. R.; Zare, A.;
at 50 °C under Aqueous Media
Azimi, S. B.; Asgari, Z.; Hasaninejad, A. C. R. Chim. 2012, 15, 719.
(18) Zare, A.; Yousofi, T.; Moosavi-Zare, A. R. RSC. Adv. 2012, 2, 7988.
Yield (%)a
(19) Khazaei, A.; Zolfigol, M. A.; Moosavi-Zare, A. R.; Asgari, Z.;
Shekouhy, M.; Zare, A.; Hasaninejad, A. RSC. Adv. 2012, 2, 8010.
(20) Zolfigol, M. A.; Khakyzadeh, V.; Moosavi-Zare, A. R.; Chehardoli,
G.; Derakhshan-Panah, F.; Zare, A.; Khaledian, O. Scientia
Iranica: Trans. C: Chem. Chem. Engin. 2012, 19, 1584.
Entry
Amount of chlorobenzene (mmol) Time (min)
1
2
3
4
1
5
2
2
82
82
80
79
70
10
15
20
2
(
(
(
21) Zare, A.; Abi, F.; Moosavi-Zare, A. R.; Beyzavi, M. H.; Zolfigol, M.
4
A. J. Mol. Liq. 2013, 178, 113.
22) Khazaei, A.; Zolfigol, M. A.; Moosavi-Zare, A. R.; Zare, A. Scientia
Iranica: Trans. C: Chem. Chem. Engin. 2010, 17, 31.
23) Zolfigol, M. A.; Khazaei, A.; Moosavi-Zare, A. R.; Zare, A.; Kruger,
H. G.; Asgari, Z.; Khakyzadeh, V.; Kazem-Rostami, M. J. Org.
Chem. 2012, 77, 3640.
5
10
a
Isolated yield.
In summary, we have introduced a novel and interesting
SAFIS ([Dsim]Cl) as a green and highly efficient reagent for
the sulfonation of aromatic compounds at 50 °C in aqueous
medium. The acidic catalyst and the source of in situ gener-
ation of H SO are present in a single compound that also
(24) Zolfigol, M. A.; Khazaei, A.; Moosavi-Zare, A. R.; Zare, A.; Asgari,
Z.; Khakyzadeh, V.; Hasaninejad, A. J. Ind. Engin. Chem. 2013, 19,
721.
(
(
(
25) Moosavi-Zare, A. R.; Zolfigol, M. A.; Noroozizadeh, E.; Tavasoli,
M.; Khakyzadeh, V.; Zare, A. New J. Chem. 2013, 37, 4089.
26) Zolfigol, M. A.; Vahedi, H.; Azimi, S.; Moosavi-Zare, A. R. Synlett
2
4
30
serves as the solvent and ionic liquid.
2013, 24, 1113.
27) Zare, A.; Hekmat-Zadeh, T.; Mirzaei-Monfared, S.; Merajoddin,
M.; Torabi-Monfared, H.; Zolfigol, M. A.; Moosavi-Zare, A. R.;
Rostami, E.; Mokhlesi, M.; Derakhshan-Panah, F.; Porbahi, S.;
Balandeh, S. S. Afr. J. Chem. 2012, 65, 63.
References
(1) Katritzky, A. R.; Kim, M. S.; Fedoseyenko, D.; Widyan, K.; Siskin,
M.; Francisco, M. Tetrahedron 2009, 65, 1111.
(
28) Khazaei, A.; Zolfigol, M. A.; Moosavi-Zare, A. R.; Zare, A.;
Ghaemi, E.; Khakyzadeh, V.; Asgari, Z.; Hasaninejad, A. Scientia
Iranica: Trans. C: Chem. Chem. Engin. 2011, 18, 1365.
(2) Cerfontain, H. J. A.; Schaasberg, Z. R. H.; Coombes, R. G.;
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1173.
(
(
(
(
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(30) General Sulfonation Procedure (Table 1)
To a round-bottomed flask (10 mL) containing of 1,3-disulfonic
acid imidazolium chloride ([Dsim]Cl) (2 mmol, 0.513 g) were
added water (2 mmol, 0.036 g) and the aromatic substrate (2
mmol). The reaction mixture was stirred at 50 °C for the requi-
site time. After the reaction was complete (monitored with
TLC), CH Cl (10 mL) was added and the reaction mixture
6) Hajipour, A. R.; Mirjalili, B. B. F.; Amin, Z.; Leila, K.; Ruoho, A. E.
Tetrahedron Lett. 2004, 45, 6607.
2
2
stirred for 2 min. The organic solvent was removed, and the
product was purified by short column chromatography.
(
(
7) Wuts, P. G. M.; Wilson, K. E. Synthesis 1998, 1593.
8) Aleboyeh, H.; Walter, S.; Aleboyeh, A.; Ladhari, N. Org. Process
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2
,4,6-Trimethylbenzenesulfonic Acid (1)
6
R = 0.39 (EtOAc–n-hexane, 2:8); mp 73–75 °C (lit. 74–76 °C). IR
f
(9) Smith, K.; Duanjie, H. J. Org. Chem. 1996, 61, 1530.
(
KBr): 3394, 3092, 3060, 2923, 1653, 1592, 1374, 1188 cm–1. 1H
(
(
10) Umemoto, T.; Tomozwaza, G. J. Org. Chem. 1995, 60, 6563.
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NMR (90 MHz, DMSO-d ): δ = 2.13 (s, 3 H), 2.57 (s, 6 H), 6.74 (s,
6
2
H), 11.34 (s, 1 H) ppm.
3
,4-Dimethylbenzenesulfonic Acid (3)
(
(
(
(
(
12) Dutov, M. D.; Serushkina, O. V.; Shevelev, A. Russ. J. Org. Chem.
6
R = 0.34 (EtOAc–n-hexane, 2:8); mp 80–82 °C (lit. 80–84 °C). IR
f
2
007, 43, 1167.
13) Shefer, N.; Carmeli, M.; Rozen, S. Tetrahedron Lett. 2007, 48,
178.
–
1 1
(KBr): 3390, 2989, 2946, 1671, 1452, 1220 cm . H NMR (90
MHz, DMSO-d ): δ = 2.17 (s, 6 H), 7.02–7.37 (m, 3 H), 14.52 (s, 1
6
8
H) ppm.
14) Zolfigol, M. A.; Khazaei, A.; Moosavi-Zare, A. R.; Zare, A. Org.
Prep. Proced. Int. 2010, 42, 95.
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Chem. Soc. 2010, 7, 646.
16) Zolfigol, M. A.; Khazaei, A.; Moosavi-Zare, A. R.; Zare, A.;
Khakyzadeh, V. Appl. Catal., A 2011, 400, 70.
4
-Bromobenzenesulfonic Acid (9)
6
Rf = 0.62 (EtOAc–n-hexane, 2:8); mp 102–104 °C (lit. 103–
–1
.
1H NMR
105 °C). IR (KBr): 3382, 3136, 3090, 1567, 1006 cm
(
90 MHz, DMSO-d ): δ = 7.15 (s, 4 H), 13.6 (s, 1 H) ppm.
6
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Georg Thieme Verlag Stuttgart · New York — Synlett 2016, 27, A–C