Abstract
An improved procedure for the synthesis of 3,4-ethylenedioxythiophene is reported starting from ethyl chloroacetate. Reaction with sodium sulfide gave diethyl thiodiglycolate which was then reacted with diethyl oxalate, and then 1,2-dibromoethane to give 2,5-dicarbethoxy-3,4-ethylenedioxythiophene. Hydrolysis, and decarboxylation gave 3,4-ethylenedioxythiophene in 16% overall yield. The structures of the key intermediates in synthetic routes were confirmed, and every step was optimised, to give a procedure suitable for large-scale industrial production.
Keywords
References
1.
Groenendaal L.B.
,
Jonas F.
,
Freitag D.
,
Pielartzik H.
, and
Reynolds J.R.
, Adv. Mater. , 2000 , 12 , 481 .
2.
Jonas F.
, and
Krafft W.
, EP440957 , 1991 .
3.
Weijtens C.H.L.
,
van Elsbergen V.
,
de Kok M.M.
, and
de Winter S.H.P.M.
, Org. Electron. , 2005 , 6 , 97 .
4.
Pettersson L.A.A.
,
Ghosh S.
, and
Inganas O.
, Org. Eelectron. , 2002 , 3 , 143 .
5.
Jeong Y.S.
,
Goto H.
,
Reynolds J.R.
, and
Akagi K.
, Curr. Appl. Phys. , 2006 , 6 , 956 .
6.
Stenger-Smith J.D.
, Prog. Polym. Sci. , 1998 , 23 , 57 .
7.
von Kieseritzky F.
,
Allared F.
,
Dahstedt E.
, and
Hellberg J.
, Tetrahedron Lett. , 2004 , 45 , 6049.
8.
Kyrides L.P.
, and
Zienty F.B.
, US2262686 , 1941 .
9.
Frontana-Uribe B.A.
, and
Heinze J.
, Tetrahedron Lett. , 2006 , 47 , 4635 .
10.
Overberger C.G.
, and
Lal J.
, J. Am. Chem. Soc. , 1951 , 73 , 2956 .
11.
Jonas F.
, DE10029078 , 2001 .
12.
Coffey M.
,
McKellar B.R.
,
Reinhardt B.A.
,
Nijakowski T.
, and
Feld W.A.
, Synth. Commun. , 1996 , 26 , 2205 .
13.
Turnbull S.G.
, US2453103 , 1948 .
14.
Fager E.W.
, J. Am. Chem. Soc. , 1945 , 67 , 2217 .
15.
Woon P.B.
,
Young S.K.
,
Hee J.H.
, and
Sang G.J.
, US0147765 , 2004 .
16.
Nie G.M.
,
Qu L.Y.
,
Xu J.K.
, and
Zhang S.S.
, Electrochim. Acta , 2008 , 53 , 8351 .