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DOI: 10.1055/s-2003-39311
Electrooxidation of Alcohols in a Disperse System with N-Oxyl-immobilized Polyethylene Particles as Disperse Phase and Aqueous NaHCO3/NaBr as Disperse Media: A Totally Closed Electrolysis System
Publication History
Publication Date:
20 May 2003 (online)
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Abstract
Electrooxidation of alcohols was performed successfully in a disperse system with N-oxyl immobilized polyethylene particles as disperse phase and an aqueous saturated NaHCO3 solution involving 20 wt% NaBr as disperse media. The N-oxyl immobilized polyethylene particles were prepared by heating a suspension of polyethylene particles (3 × 3 × 0.02 mm3) in fuming nitric acid at 80 °C for 1 h followed by treatment with 4-amino-2,2,6,6-tetramethylpyperidine-1-oxyl in chlorobenzene in the presence of DCC. Recycle use of the N-oxyl-immobilized polyethylene particles and the aqueous media was performed successfully without significant change of the yields of the products and current efficiency, thereby offering a totally closed electrolysis system.
Key words
electrooxidation - alcohol - N-oxyl - polyethylene particles - aqueous disperse media - disperse system
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1a
Semmelhack MF.Chou CS.Cortes DA. J. Am. Chem. Soc. 1983, 105: 4492 -
1b
Ma Z.Huang Q.Bobbitt JM. J. Org. Chem. 1993, 58: 4837 -
1c
Yanagisawa Y.Kashiwagi Y.Kurashima F.Anzai J.Osa T.Bobbitt JM. Chem. Lett. 1996, 1043 -
1d
Kashiwagi Y.Yanagisawa Y.Kurashima F.Anzai J.Osa T.Bobbitt JM. J. Chem. Soc., Chem. Commun. 1996, 27: 45 -
1e
Kashiwagi Y.Kurashima F.Kikuchi C.Anzai J.Osa T.Bobbitt JM. Tetrahedron Lett. 1999, 40: 6469 ; and references cited therein - CH2Cl2/H2O two phase system for N-oxyl-mediated electrooxidation of alcohols:
-
2a
Inokuchi T.Matsumoto S.Nishiyama T.Torii S. J. Org. Chem. 1990, 55: 462 -
2b
Torii S.Inokuchi T.Matsumoto S.Saeki T.Oki T. Bull. Chem. Soc. Jpn. 1990, 63: 852 -
2c
Inokuchi T.Matsumoto S.Torii S. J. Org. Chem. 1991, 56: 2416 -
2d
Inokuchi T.Liu P.Torii S. Chem. Lett. 1994, 1411 -
2e
Kuroboshi M.Yoshihisa H.Cortona MN.Kawakami Y.Gao Z.Tanaka H. Tetrahedron Lett. 2000, 41: 8131 -
2f Electrooxidation of carbohydrate
in aqueous solution:
Schnatbaum K.Schafer HJ. Synthesis 1999, 864 - 3
Tanaka H.Kawakami Y.Goto K.Kuroboshi M. Tetrahedron Lett. 2001, 42: 445 - 4 Recently, transition metal/TEMPO-catalyzed
aerobic oxidation has been reported as an environmentally benign procedure
for oxidation of alcohols. See for example:
Sheldon RA.Arends IWCE.Brink G.-JT.Dijksman A. Acc. Chem. Res. 2002, 35: 774 -
5a
Killer A.Udagawa YJ. Polym. Sci. 1970, 8: 19 -
5b
Shimamura K.Munesawa Y.Uchida T.Hikasa N. Polym. Adv. Tech. 2002, 13: 205
References
IR spectra of the polymer particles showed a characteristic absorption band at 1712 cm-1 due to carboxylic acid, which disappeared during the subsequent treatment with 4-amino-2,2,6,6-tetramethylpiperidine-N-oxyl.
7Carried out on a Yanaco GC 6800 with a Quadrex Corporation fused silica glass capillary column (methyl phenyl 5: 25 m × 0.25 mm i.d.). Column 100 ºC, injector 270 ºC, detector 300 ºC, carrier gas, He; flow rate, 26 mL/min.
8Electrogenerated iodine species, e. g., I2 and IO-, would not act as the oxidant for generation of N-oxoammonium ion from N-oxyl.