1-Butyl-3-Methylimidazolium Bromide Promoted Selectively Oxidation of Sulfur Compounds by NaBrO3

Document Type: Research Article


Department of Chemistry, Shahid Beheshti University, P.O. Box 19396-4716 Tehran, I.R. IRAN


1-Butyl-3-methylimidazolium bromide ([bmim]Br) as an ionic liquid promoted selectively oxidation of aliphatic and aromatic sulfides to the corresponding sulfoxides and the oxidative coupling of thiols to disulfides by NaBrO3 in excellent yields under neutral conditions.


Main Subjects

[1] Prilezhaeva E.N., Rearrangements of Sulfoxides and Sulfones in the Total Synthesis of Natural Compounds, Russ. Chem. Rev., 70, p. 897 (2001).

[2] Carreno M.C., Applications of Sulfoxides to Asymmetric Synthesis of Biologically Active Compounds, Chem. Rev., 95, p. 1717 (1995).

[3] Fernandez I., Khiar N., Recent Developments in the Synthesis and Utilization of Chiral Sulfoxides, Chem. Rev., 103, p. 3651 (2003).

[4] Thorarensen A., Palmgren A., Itami K., Backvall J.E., Palladium(II)-Catalyzed Asymmetric 1,4-Oxidation of 2-Phenyl-1,3-Cyclohexadiene, Tetrahedron Lett., 38, p. 8541 (1997).

[5] Padmanabhan S., Lavin R.C., Durant G.J., Asymmetric Synthesis of a Neuroprotective and Orally Active N-Methyl-d-Aspartate Receptor Ion-Channel Blocker, CNS 5788, Tetrahedron: Asymm., 11, p. 3455 (2000).

[6] Rowlands J.G., Chiral Sulfoxide Ligands in Catalytic Asymmetric Cyanohydrin Synthesis, Synlett, 236 (2003).

[7] Dorta R., Shimon L.J.W., Milstein D., Dimethylsulfoxide as a Ligand for RhI and IrI Complexes-Isolation, Structure and Reactivity Towards X=H Bonds (X=H, OH, OCH3), Chem. Eur. J., 9, p. 5237 (2003).

[8] (a) Khenkin A.M., Neumann R., Oxygen Transfer from Sulfoxides: Oxidation of Alkylarenes Catalyzed by A Polyoxomolybdate, [Pmo12O40]3-, J. Am. Chem. Soc., 124, p. 4198 (2002).

(b) Kaczorowska K., Kolarska Z., Mitka K., Kowalski P., Oxidation of Sulfides to Sulfoxides, Part 2: Oxidation by Hydrogen Peroxide, Tetrahedron, 61, p. 8315 (2005).

[9] Olah G.A., Gupta B.G.B., Fung A.P., Synthetic Methods and Reactions; 951. Ceric Ammonium Nitrate-Catalyzed Oxidative Cleavage of Alkyl and Silyl Ethers with Sodium Bromate, Synthesis, 897 (1980).

[10] (a) Kikuchi D., Sakaguchi S., Ishii Y., An Alternative Method for the Selective Bromination of Alkylbenzenes Using NaBrO3 / NaHSO3 Reagent, J. Org. Chem., 63, p. 6023 (1998).

(b) Biernstiel M., Dhondt P.J., Schalaf M., Investigation Into the Selective Oxidation of Vicinal Diols to a-Hydroxy Ketones with the NaBrO3 / NaHSO3 Reagent: pH Dependence, Stoichiometry, Substrates and Origin of Selectivity, Tetrahedron, 61, p. 4911 (2005).

(c) Takes K., Masuda O., Kaf O., Nishiyama Y., Oxidative Esterification of Primary Alcohols by NaBrO3 / NaHSO3 Reagent in Aqueous Medium, Sakguchi S., Ishii Y., Chem. Lett., 871 (1995).

(d) Sakguchi S., Kikuchi D., Ishii Y,. Oxidation of Diols and Ethers by NaBrO3 / NaHSO3 Reagent, Bull. Chem. Soc. Jpn., 70, p. 2561 (1997).

[11] Kajigaeshi S., Nakagawa T., Nakasaki N., Yamasaki H., Fujisaki S., Oxidation of Alcohols and Ethers Using Sodium Bromate-Hydrobromic Acid System, Bull. Chem. Soc. Jpn., 59, p. 747 (1986).

[12] (a) Ho T.L., Cerium(IV)-Oxidation with a Dual Oxidant System; Reactiono f Some Arylamethanols, Synthesis, 936 (1978).

(b) Tomioka H.O., Nozaki K.H., Cerium Catalyzed Selective Oxidation of Secondary Alcohols in the Presence of Primary Ones, Tetrahedron Lett., 23, p. 539 (1982).

(c) Hajipour A.R., Khazdooz L., Ruoho A.E., Selective and Efficient Oxidation of Sulfides to Sulfoxides Using Ceric Ammonium Nitrate (CAN)/Bronsted Acidic Ionic Liquid, Phosphorus, Sulfur, and Silicon, 178, p. 705 (2009).

[13] (a) Wang Y., Zhao Y., Wang X., Duan Z., Synthesis of New-Typed α,β- Unsaturated Acyl Azo zompounds with NaBrO3/H2SO4 as the Oxidative System, Synth. Commun., 32, p. 1781 (2002).

(b) Hoist G., The Oxidation of Thioglycol by Iodate or Bromated Ions in Solutions of Sulfuric Acid, Kgl. Fysiogrof. Sallskap. Lund, 10, p. 63  (1940) (Chem. Abst. 1941, 35, 78089).

[14] Metsger L., Bittner S., Autocatalytic Oxidation of Ethers with Sodium Bromate, Tetrahedron, 56, p. 1905 (2000).

[15] Shaabani A., Bazgir A., Teimouri M.B., Conversion of Alkylbenzenes to Carbonyl Compounds by NaBrO3 in the Presence of NH4Cl and Bu4NHSO4, Synth. Commun., 32, p. 675 (2002).

[16] Chatterji A. C., Roy S.K.Z., Mechanism of Oxidation of Simple Organic Molecules (XXIV) Oxidation of Methyl, Ethyl, Propyl, and Isopropyl Alcohols by Bromate Ion in Acid Media, Phys. Chem., 250, p. 137 (1972) (Chem. Abst. 1972, 77, 39201z).

[17] Shaabani A., Bazgir A., Soleimani K., Salehi P., Solvent Effects in the Oxidation of Sulfides with NaBrO3/Mg(HSO4)2, Synth. Commun., 33, p. 2935 (2003).

[18] Shaabani A., Soleimani K., Bazgir A., Silica Sulfuric Acid Catalysis the Oxidation of Organic Compounds with Sodium Bromate, Synth. Commun., 34, p. 3303 (2004).

(b) Shaabani A., Lee D.G., Selective Oxidation of Sulfides Under Solvent-Free Conditions, Sulfur Lett., 26, p. 43 (2003).

(b) Shaabani A., Teimouri M.B., Safaei H.R., A Simple and Efficient Procedure for Oxidation of Sulfides to Sulfoxides by Hexamethylenetetramine-Bromine Complex(HMTAB), Synth. Commun., 30, p. 265 (2000).

(c) Shaabani A., Karimi A.R., Oxidation Deprotection of Trimethylsilyl Ethers to Carbonyl Compounds by NaBrO3-NH4Cl Reagent in Aqueous Acetonitrile, Synth. Commun., 31, p. 759 (2001).

[21] Kikuchi D., Sakaguchi S., Ishii Y., An Alternative Method for the Selective Bromination of Alkylbenzenes Using NaBrO3/NaHSO3 Reagent, J. Org. Chem., 63, p. 6023 (1998).

[22] Earle M.J., Seddon K.R., Ionic Liquids. Green Solvents for the Future, Pure Appl. Chem., 72, p. 1391 (2000).

[23] Welton T., Room-Temperature Ionic Liquids. Solvents for Synthesis and Catalysis, Chem. Rev., 99, p. 2071 (1999).

[24] Wasserscheid P., Keim W., Ionic Liquids-New “Solutions” for Transition Metal Catalysis, Angew. Chem. Int. Ed., 39, p. 3773 (2000).

[25] Dupont J., de Souza R.F., Suarez P.A.Z., Ionic Liquid (Molten Salt) Phase Organometallic Catalysis, Chem. Rev., 102, p. 3667 (2002).

[26] Sheldon R., Catalytic Reactions in Ionic Liquids, Chem. Commun, 2399 (2001).

[27] Wasserscheid P., Welton T., "Ionic Liquids in Synthesis", Wiley-VCH: Weinheim (2002).

[28] Gordon C.M., New Developments in Catalysis Using Ionic Oiquids, Appl. Catal. A, 222, p. 101 (2001).

[29] Muzart J., Ionic Liquids as Solvents for Catalyzed Oxidations of Organic Compounds, Adv. Synth. Catal., 348, p. 275 (2006).

[30] Shaabani A., Bazgir A., Abdoli M., A New and Efficient Aerobic Oxidation of Aldehydes to Carboxylic Acids with Singlet Oxygen in the Presence of Porphyrin Sensitizers and Visible Light, Synth. Commun., 32, p. 683 (2002).

[31] Shaabani A., Bazgir A., Teimouri F., Lee D.G., Selective Oxidation of Alkylarenes in Dry Media with Potassium Permanganate Supported on Montmorillonite K10, Tetrahedron Lett., 43, p. 5165 (2002).

[32] Shaabani A., Lee D.G., Solvent Free Permanganate Oxidations, Tetrahedron Lett., 42, p. 5833 (2001).

[33] Shaabani A., Mirzaei P., Naderi S., Lee D.G., Green Oxidations. The Use of Potassium Permanganate Supported on Manganese Dioxide, Tetrahedron, 60, p. 11415 (2004).

[34] Shaabani A., Safaei H.R., Bazgir A., Oxidation of Sulfides to Sulfoxides by NaBrO3 -NH4Cl in Aqueous Acetonitrile, Iran. J. Chem. Chem. Eng., 19, p. 47 (2000).

[35] Baciocchi E., Lanzalunga O., Malandrucco S., Oxidation of Sulfides by Peroxidases. Involvement of Radical Cations and the Rate of the Oxygen Rebound Step, J. Am. Chem. Soc., 118, p. 8973 (1996).

[37] Firouzabadi H., Sardarian A., Badparva H., Oxidation of Organic Compounds with Tetrabutylammonium Periodate in the Presence of Lewis Acids in Aprotic Organic Solvents, Bull. Chem. Soc. Jpn., 69, p. 685 (1996).

[38] Firouzabadi H., Seddighi M., Conversion of Sulfides to Their Corresponding Sulfoxides with Barium Permanganate Ba(MnO4)2 Under Non-Aquesous Conditions, Synth. Commun., 21, p. 211 (1991).

[39] Mashraqui S.H., Mudaliar C.D., Karnik M.A., Bi(NO3)3.5H2O: A Convenient Reagent for Selective Oxidation of Sulfides to Sulfoxides, Synth. Commun., 28, p. 939 (1998).

[40] Karimi B., Ghoreishi-Nezhad M., Clark J.H., Selective Oxidation of Sulfides to Sulfoxides Using 30% Hydrogen Peroxide Catalyzed with a Recoverable Silica-Based Tungstate Interphase Catalyst, Org. Lett., 7, p. 625 (2005).

[41] Das R., Chakraborty D., Cu(II)-Catalyzed Oxidation of Sulfides, Tetrahedron Lett., 51, p. 6255 (2010).

[42] Firouzabadi H., Sardarian A., Badparva H., Oxidation of Organic Compounds with Tetrabutylammonium Periodate in the Presence of Lewis Acids in Aprotic organic Solvents, Bull. Chem. Soc. Jpn,69, 685 (1996).

[43] "Handbook of Chemistry and Physics", 70th Ed., CRC Press, (1989-1990).

[44] Searles S.J., Hays H.Y., Notes - Oxidation of Organic Sulfides with Dimethyl Sulfoxide, J. Org. Chem., 23, p. 2028 (1958).

[45] "Dictionary of Organic Compounds", 6th Ed., Chapman and Hall, London, (1966).

[46] Orito K., Hatakeyama T., Takeo M., Suginoma H., Oxidation with Mercury(II) Oxide-Iodine Reagent: Selective Oxidation of Sulfides to Sulfoxides, Synthesis, 1357 (1995).

[47] Ho T.-L., Wong C.M., Dethioacetalization via S-Methylation, Synthesis, 561 (1972).

[48] Iranpoor N., Firouzabadi H., Zolfigol M.A., Dinitrogen Tetroxide Copper Nitrate Complex [Cu(NO3)2.N2O4] as a New Nitrosating Agent for Catalytic Coupling of Thiols via Thionitrite, Synth. Commun., 28, p. 367 (1998).

[49] Lide D.R.; "CRC Handbook of Chemistry and Physics", 74th Ed., CRC Press, Ann Arbor, (1993).

[50] "The Sadtler Standard Spectra, NMR", Sadtler Research Laboratories, INC, 12327M, (1972). CA, 52, 4543 (1958).

[51] Wallace T.J., Reactions of Thiols with Sulfoxides. I. Scope of the Reaction and Synthetic Applications, J. Am. Chem. Soc., 86, p. 2018 (1964).