{-N⁺(CH₃)₂CH₂CH₂N⁺[(CH₃)₂](CH₂)₄-}_n S₂O₈ ^2-: A Selective and Recyclable ­Reagent for Oxidation of Alcohols and Hydroquinones in Water

Abstract

This article describes the oxidation of alcohols and ­hydroquinones in water using polymer-supported peroxodisulfate, which has been prepared by mixing an aqueous solution of 2,4-ionene with an aqueous solution of potassium peroxodisulfate at room temperature.

Key words

peroxodisulfate - alcohols - hydroquinones - oxidation

References and Notes

• 1 Fieser LF. Fieser M. Reagents for Organic Synthesis   Vol. 1-11:  Wiley; New York: 1967-1984. 
• 2a Anastas PT. Williamson TC. Green Chemistry: Frontiers in Benign Chemical Synthesis and Processes   Oxford University Press; Oxford: 1998. 
• 2b Curzons AD. Constable DCJ. Mortimer DN. Cunningham VL. Green Chem.  2001,  3:  1 
• 3a Corey EJ. Boger DL. Tetrahedron Lett.  1978,  19:  2461 
• 3b Corey EJ. Schmidt G. Tetrahedron Lett.  1979,  20:  399 
• 3c Guziec FS. Luzzio FA. Synthesis  1980,  691 
• 3d Bhattacharjee MN. Chaudhuri MK. Dasgupta HS. Roy N. Synthesis  1982,  588 
• 3e Santeniello E. Milani F. Casati R. Synthesis  1983,  749 
• 3f Rajkumar GA. Murugesan V. Synth. Commun.  1999,  29:  2105 
• 3g Tajbakhsh M. Ghaemi M. Sarabi M. Ghassemzadeh M. Heravi MM. Monatsh. Chem.  2000,  131:  1213 
• 3h Mahjoub AR. Ghammami Sh. Kassaee MZ. Tetrahedron Lett.  1975,  16:  2647 
• 3i Tajbakhsh M. Hosseinzadeh R. Yazdani-Niaki M. J. Chem. Res., Synop.  2002,  10:  508 
• 3j Tajbakhsh M. Hosseinzadeh R. Yazdani-Niaki M. Tetrahedron Lett.  2002,  43:  9413 
• 3k Tajbakhsh M. Hosseinzadeh R. Sadatshahabi M. Synth. Commun.  2005,  35:  1547 
• 3l Tajbakhsh M. Lakouraj MM. Yadoolahzadeh K. Phosphorus, Sulfur Silicon Relat. Elem.  2005,  180:  2431 
• 3m Shirini F. Mohammadpoor-Baltork I. Hejazi Z. Heravi P. Bull. Korean Chem. Soc.  2003,  24:  517 
• 3n Alessandro N. Liberatore L. Tonucci L. Morvillo A. Bressan M. J. Mol. Catal. A: Chem.  2001,  175:  83 
• 3o Firozabadi H. Salehi D. Mohamadpour-Baltork I. Bull. Chem. Soc. Jpn.  1991,  65:  2879 
• 3p Jung JC. Choi HC. Kim YH. Tetrahedron Lett.  1993,  7:  3581 
• 3q Hajipour AR. Mohammadpour-Baltork I. Kianfar G. Bull. Chem. Soc. Jpn.  1998,  71:  2655 
• 3r Mohammadpoor I. Hajipour AR. Mohammadi H. Bull. Chem. Soc. Jpn.  1998,  71:  1649 
• 4 Hinzen A. Lenz K. Ley SV. Synthesis  1999,  977 
• 5 Tamami B. Godarzian N. Eur. Polym. J.  1992,  28:  1035 
• 6 Godarzian N. Ghahramani P. Hosini S. Polym. Int.  1996,  39:  61 
• 7 Suresh S. Skaria S. Pontrathnam S. Synth. Commun.  1996,  26:  2113 
• 8 Minghu W. Guichun Y. Zuxing C. React. Funct. Polym.  2000,  44:  97 
• 12 John W. Son I. Polym. Lett. Ed.  1977,  15:  31 
• 13 House DA. Chem. Rev.  1962,  185 

9

Preparation of {-N ⁺ (CH ₃ ) ₂ CH ₂ CH ₂ N ⁺ [(CH ₃ ) ₂ ](CH ₂ ) ₄ -} _n S ₂ O ₈ ^²- (P-S ₂ O ₈ ). To an aqueous solution of polymer (1 g, 5 mL of H₂O) was added a solution of K₂S₂O₈ (1.62 g, 6 mmol in 30 mL of H₂O). The mixture was stirred at r.t. for 30 min. The resulting white solid was filtered, washed with distilled H₂O (10 mL) and dried over CaCl₂ in a desiccator under vacuum. The content of active oxidizing agent (S₂O₈ ^2-) was determined by titration. [8]

10

Typical Procedure for Oxidation of Alcohols and Hydroquinone with P-S ₂ O ₈ .
A mixture of alcohol or hydroquinone (1 mmol), H₂O (10 mL) and P-S₂O₈ (0.36 g, ca. 1 mmol) was placed in a 25-mL round-bottom flask and was stirred and heated to reflux. After completion of the reaction (monitored by TLC), the reaction mixture was cooled, and extracted with Et₂O (3 × 10 mL). The combined organic layers were washed with brine, dried over anhyd Na₂SO₄, and solvent evaporated under reduced pressure. The crude product was purified by column chromatography on silica gel to afford pure material.

11

Typical Procedure for Recycled P-S ₂ O ₈ .
The solvated polymer in aqueous phase after completion of the reaction was washed with Et₂O and recycled with added solution of K₂S₂O₈ (in H₂O). The resulting white solid product was filtered, washed with Et₂Ο (3 × 10 mL) and cooled distilled H₂O (10 mL) and dried over CaCl₂ in a desiccator under vacuum for subsequent reaction.