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Corresponding Author

Cheng-chu ZENG(zengcc@bjut.edu.cn)

Abstract

To effectively recover redox catalyst and supporting electrolyte, a novel ternary composite consisting of ionic liquid-supported TEMPO, polymeric ionic-liquid and carbon black was prepared. The ionic-liquid supported redox catalyst TEMPO-IL-BF4 was firstly synthesized from 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl, and followed by the reaction of polydimethyldiallylammonium chloride (PDDA) and bis(trifluoromethane)sulfonimide lithium salt (LiTFSI) to form poly[diallyldimethylammonium bis(trifluoromethanesulfonyl)imide] (PDDA(Tf2N)). A combination of the above mentioned two synthesized materials and carbon black afforded to obtain the ternary composite, which was used as the recoverable supporting electrolyte and mediator for the electrochemical oxidation of alcohol. The results indicate that various alcohols could be oxidized efficiently to the corresponding aldehydes or ketones with the more than 80% yields in the presence of the ternary composite under electrochemical conditions. In addition, the composite could be recovered with 95% recovery after being used for 4 times in experiments. The development of the ternary composite provides an efficient and sustainable approach for the recovery of supporting electrolyte and redox catalyst.

Graphical Abstract

Keywords

ionic liquid-supported TEMPO as redox catalyst, polymeric ionic liquid, recoverable ternary composite

Publication Date

2017-06-29

Online Available Date

2017-03-02

Revised Date

2017-02-13

Received Date

2016-11-15

References

[1] Ma C A (马淳安). Introduction of organic electrochemistry (有机电化学合成导论)[M]. Beijing: Science Publisher, 2002, 5-6.

[2] Huang P Q (黄培强). Green synthesis: an emerging frontier in organic synthesis[J]. Progress in Chemistry (化学进展), 1998, 10: 265-272.

[3] Yoo S J, Li L J, Zeng C C, et al. Polymeric ionic liquid and carbon black composite as a reusable supporting electrolyte: modification of the electrode surface[J]. Angewandte Chemie International Edition, 2015, 54(12): 3744-3747.

[4] Dijksman A, Marino-González A, Mairata i Payeras A., et al. Efficient and selective aerobic oxidation of alcohols into aldehydes and ketones using ruthenium/TEMPO as the catalytic system[J]. Journal of the American Chemical Society, 2001, 123(28): 6826€“6833.

[5] Rohlmann R, Stopka T, Richter H, et al. Iron-catalyzed oxidative tandem reactions with TEMPO oxoammonium salts: synthesis of dihydroquinazolines and quinolones[J]. The Journal of Organic Chemistry, 2013, 78(12): 6050-6064.

[6] Qian W X, Jin E L, Bao W L, et al. Clean and selective oxidation of alcohols catalyzed by ion-supported TEMPO in water[J]. Tetrahedron, 2006, 62 (4): 556€“562.

[7] Mitsui M, Takeda K, Kobori Y, et al. Unusually large dynamic electron polarization in an O2(1Δg)ˆ’2,2,6,6-Tetramethylpiperidine-1-oxyl radical system[J]. The Journal of Physical Chemistry, 2004, 108(7): 1120-1126.

[8] Mehnert C P, Cook R A, Dispenziere N C, et al. Supported ionic liquid catalysis - a new concept for homogeneous hydroformylation catalysis[J]. Journal of the American Chemical Society, 2002, 124(44): 12932-12933.

[9] Miao W S, Chan T H. Ionic-liquid-supported peptide synthesis demonstrated by the synthesis of leu(5)-enkephalin[J]. The Journal of Organic Chemistry, 2005, 70(8): 3251-3255.

[10] Grotli M, Gotfredsen C H, Rademann J, et al. Physical properties of poly(ethylene glycol) (PEG)-based resins for combinatorial solid phase organic chemistry: a comparison of PEG-cross-linked and PEG-grafted resins[J]. Journal of Combinatorial Chemistry, 2000, 2(2): 108-119.

[11] Sun Q (孙茜), Liu Y L (刘元兰), Lu J X (陆嘉星). Application of ionic liquids in electrochemistry[J]. Chemistry Bulletin (化学通报), 2003, 66(2): 112-114.

[12] Zhu Y G, Zhu Y, Zeng H Y, et al. A promising electro-oxidation of methyl-substituted aromatic compounds to aldehydes in aqueous imidazole ionic liquid solutions[J]. Journal of Electroanalytical Chemistry, 2015, 751: 105-110.

[13] Yuan Y, Shi X, Liu W. Transition metal-free chemoselective aerobic oxidations of sulfides and alcohols with potassium nitrate and pyridinium tribromide or bromine[J]. Synlett, 2011, 4: 559-564.

[14] Cacchi S, Fabrizi G., Goggiamani A. Palladium-catalyzed synthesis of aldehydes from aryl iodides and acetic formic anhydride[J]. Journal of Combinatorial Chemistry, 2004, 6(5): 692€“694.

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