Regioselective Sulfonation of Aromatic Compounds over 1,3-Disulfonic Acid Imidazolium Chloride under Aqueous Media

Abstract

1,3-Disulfonic acid imidazolium chloride ([Dsim]Cl), as a Brønsted acidic ionic liquid, is introduced for the sulfonation of aromatic compounds by in situ generation of sulfuric acid at 50 °C under mild conditions and in aqueous medium.

Key words

sulfonation - ionic liquid - sulfonic acid functionalized imidazolium salt (SAFIS) - aqueous medium

• References

• 1 Katritzky AR, Kim MS, Fedoseyenko D, Widyan K, Siskin M, Francisco M. Tetrahedron 2009; 65: 1111
• 2 Cerfontain HJ. A, Schaasberg ZR. H, Coombes RG, Hadjigeorgion P, Tucker GP. J. Chem. Soc., Perkin Trans. 2 1985; 659
• 3 Qureshi ZS, Deshmukh KM, Jagtap SR, Nandurkar NS, Bhanage BM. Ultrason. Sonochem. 2009; 16: 308
• 4 Corby BW, Gary AD, Meaney PJ, Falvey M, Lawrence GP, Smyth TP. J. Chem. Res., Synop. 2002; 7: 326
• 5 Bochkareva TP, Yakovlev IP, Passet BV, Sheiko MA. J. Org. Chem. USSR (Engl. Transl.) 1989; 25: 1346
• 6 Hajipour AR, Mirjalili BB. F, Amin Z, Leila K, Ruoho AE. Tetrahedron Lett. 2004; 45: 6607
• 7 Wuts PG. M, Wilson KE. Synthesis 1998; 1593
• 8 Aleboyeh H, Walter S, Aleboyeh A, Ladhari N. Org. Process Res. Dev. 1997; 1: 411
• 9 Smith K, Duanjie H. J. Org. Chem. 1996; 61: 1530
• 10 Umemoto T, Tomozwaza G. J. Org. Chem. 1995; 60: 6563
• 11 Rajanna KC, Venkanna P, Kumar MS, Gopal SR. Int. J. Org. Chem. 2012; 2: 336
• 12 Dutov MD, Serushkina OV, Shevelev A. Russ. J. Org. Chem. 2007; 43: 1167
• 13 Shefer N, Carmeli M, Rozen S. Tetrahedron Lett. 2007; 48: 8178
• 14 Zolfigol MA, Khazaei A, Moosavi-Zare AR, Zare A. Org. Prep. Proced. Int. 2010; 42: 95
• 15 Zolfigol MA, Khazaei A, Moosavi-Zare AR, Zare A. J. Iran. Chem. Soc. 2010; 7: 646
• 16 Zolfigol MA, Khazaei A, Moosavi-Zare AR, Zare A, Khakyzadeh V. Appl. Catal., A 2011; 400: 70
• 17 Zolfigol MA, Khakyzadeh V, Moosavi-Zare AR, Zare A, Azimi SB, Asgari Z, Hasaninejad A. C. R. Chim. 2012; 15: 719
• 18 Zare A, Yousofi T, Moosavi-Zare AR. RSC. Adv. 2012; 2: 7988
• 19 Khazaei A, Zolfigol MA, Moosavi-Zare AR, Asgari Z, Shekouhy M, Zare A, Hasaninejad A. RSC. Adv. 2012; 2: 8010
• 20 Zolfigol MA, Khakyzadeh V, Moosavi-Zare AR, Chehardoli G, Derakhshan-Panah F, Zare A, Khaledian O. Scientia Iranica: Trans. C: Chem. Chem. Engin. 2012; 19: 1584
• 21 Zare A, Abi F, Moosavi-Zare AR, Beyzavi MH, Zolfigol MA. J. Mol. Liq. 2013; 178: 113
• 22 Khazaei A, Zolfigol MA, Moosavi-Zare AR, Zare A. Scientia Iranica: Trans. C: Chem. Chem. Engin. 2010; 17: 31
• 23 Zolfigol MA, Khazaei A, Moosavi-Zare AR, Zare A, Kruger HG, Asgari Z, Khakyzadeh V, Kazem-Rostami M. J. Org. Chem. 2012; 77: 3640
• 24 Zolfigol MA, Khazaei A, Moosavi-Zare AR, Zare A, Asgari Z, Khakyzadeh V, Hasaninejad A. J. Ind. Engin. Chem. 2013; 19: 721
• 25 Moosavi-Zare AR, Zolfigol MA, Noroozizadeh E, Tavasoli M, Khakyzadeh V, Zare A. New J. Chem. 2013; 37: 4089
• 26 Zolfigol MA, Vahedi H, Azimi S, Moosavi-Zare AR. Synlett 2013; 24: 1113
• 27 Zare A, Hekmat-Zadeh T, Mirzaei-Monfared S, Merajoddin M, Torabi-Monfared H, Zolfigol MA, Moosavi-Zare AR, Rostami E, Mokhlesi M, Derakhshan-Panah F, Porbahi S, Balandeh SS. Afr. J. Chem. 2012; 65: 63
• 28 Khazaei A, Zolfigol MA, Moosavi-Zare AR, Zare A, Ghaemi E, Khakyzadeh V, Asgari Z, Hasaninejad A. Scientia Iranica: Trans. C: Chem. Chem. Engin. 2011; 18: 1365
• 29 Moosavi-Zare AR, Zolfigol MA, Daraei M. Synlett 2014; 25: 1173
• 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 requisite time. After the reaction was complete (monitored with TLC), CH₂Cl₂ (10 mL) was added and the reaction mixture stirred for 2 min. The organic solvent was removed, and the product was purified by short column chromatography. 2,4,6-Trimethylbenzenesulfonic Acid (1) R_f = 0.39 (EtOAc–n-hexane, 2:8); mp 73–75 °C (lit.⁶ 74–76 °C). IR (KBr): 3394, 3092, 3060, 2923, 1653, 1592, 1374, 1188 cm^–1. ¹H NMR (90 MHz, DMSO-d ₆): δ = 2.13 (s, 3 H), 2.57 (s, 6 H), 6.74 (s, 2 H), 11.34 (s, 1 H) ppm. 3,4-Dimethylbenzenesulfonic Acid (3) R_f = 0.34 (EtOAc–n-hexane, 2:8); mp 80–82 °C (lit.⁶ 80–84 °C). IR (KBr): 3390, 2989, 2946, 1671, 1452, 1220 cm^–1. ¹H NMR (90 MHz, DMSO-d ₆): δ = 2.17 (s, 6 H), 7.02–7.37 (m, 3 H), 14.52 (s, 1 H) ppm. 4-Bromobenzenesulfonic Acid (9) R_f = 0.62 (EtOAc–n-hexane, 2:8); mp 102–104 °C (lit.⁶ 103–105 °C). IR (KBr): 3382, 3136, 3090, 1567, 1006 cm^–1. ¹H NMR (90 MHz, DMSO-d ₆): δ = 7.15 (s, 4 H), 13.6 (s, 1 H) ppm.