O-alkylation of disodium salt of diethyl 3,4-dihydroxythiophene-2,5-dicarboxylate with 1,2-dichloroethane catalyzed by ionic type phase transfer catalyst and potassium iodide

Huasheng Lu; Hengbo Yin; Aili Wang; Jun Shen; Xiaobo Yan; Yumin Liu; Changhua Zhang

Korean Journal of Chemical Engineering, Vol.31, No.1, 45-49, January, 2014

DOI10.1007/s11814-013-0208-3 Export Citation

O-alkylation of disodium salt of diethyl 3,4-dihydroxythiophene-2,5-dicarboxylate with 1,2-dichloroethane catalyzed by ionic type phase transfer catalyst and potassium iodide

Huasheng Lu, Hengbo Yin^†, Aili Wang, Jun Shen, Xiaobo Yan, Yumin Liu, and Changhua Zhang

Faculty of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, China

E-mail:

Diethyl 3,4-ethylenedioxythiophene-2,5-dicarboxylate was efficiently synthesized via the O-alkylation of disodium salt of diethyl 3,4-dihydroxythiophene-2,5-dicarboxylate with 1,2-dichloroethane over ionic type phase transfer catalysts, such as tetrabutyl ammonium bromide and benzyltriethyl ammonium chloride. The ionic type phase transfer catalysts showed higher catalytic activities than the nonionic type phase transfer catalysts, such as triethylamine, pyridine, 18-crown-6, and polyethylene glycol 400/600, in the O-alkylation reaction. The conversion of the disodium salt of more than 97% and the selectivity of diethyl 3,4-ethylenedioxythiophene-2,5-dicarboxylate of more than 98% were achieved when the O-alkylation reaction was synergistically catalyzed by tetrabutyl ammonium bromide and potassium iodide.

Keywords:O-alkylation;Phase Transfer Catalysis;Tetrabutyl Ammonium Bromide;Potassium Iodide;Diethyl 3,4-Ethylenedioxythiophene-2,5-dicarboxylate

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[4] Caras-Quintero D, Bauerle P, Chem. Commun., 22, 2690 (2002)

[5] Yue RR, Xu JK, Synth. Met., 162, 912 (2012)

[6] Benedetto A, Balog M, Rayah H, Le Derf F, Viel P, Palacin S, Salle M, Electrochim. Acta, 53(11), 3779 (2008)

[7] Dai Q, Li Y, Zhai L, Sun W, J. Photochem. Photobiol. A:Chem., 206, 164 (2009)

[8] Jonas F, US Patent, 6,528,662 (2003)

[9] Baik WP, Kim YS, Hong HJ, Jung SG, US Patent, 7,202,369B2 (2007)

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[14] Li HS, Li YQ, Chin. Chem. Lett., 21, 931 (2010)