4640
B. A. Frontana-Uribe, J. Heinze / Tetrahedron Letters 47 (2006) 4635–4640
yield of dibenzylated compound 5f was obtained. Due to
D.; B a¨ uerle, P. Chem. Commun. 2002, 2690–2691; (f)
Lomas, J. S.; Adenier, A.; Gao, K.; Maurel, F.; Vaisser-
mann, J. J. Chem. Soc., Perkin Trans. 2 2002, 216–224; (g)
Storsberg, J.; Schollmeyer, D.; Ritter, H. Chem. Lett.
2003, 32, 140–141; (h) Coffey, M.; McKellar, B. R.;
Reinhardt, B. A.; Nijakowski, T.; Feld, W. A. Synth.
Commun. 1996, 26, 2205–2212; (i) Turbiez, M.; Fr e` re, P.;
Roncali, J. Tetrahedron 2005, 61, 3045–3053; (j) Leriche,
P.; Blanchard, P.; Fr e` re, P.; Levillain, E.; Mabon, G.;
Roncali, J. Chem. Commun. 2006, 275–277.
the hard chromatographic separation of these two com-
0
pounds, all the other ratios between 5f and 5f were
1
determined by the H NMR signal of their benzylic pro-
tons (5f d = 5.19 ppm and 5f d = 5.33 ppm) in the crude
0
mixture obtained passing it trough a short SiO column
2
(
eluted with EtOAc/petroleum ether 40–60 ꢁC).
Acknowledgments
7. R = Me and Et: (a) Hinsberg, O. Chem. Ber. 1910, 43,
9
01–906; R = Et: (b) Overberger, C. G.; Lal, J. J. Am.
Chem. Soc. 1951, 73, 2956–5957; R = Et: (c) Gogte, V. N.;
Shah, L. G.; Tilak, B. D.; Gadekar, K. N.; Sahasrabudhe,
M. B. Tetrahedron 1967, 23, 2437–2441; R = Me: (d)
Fager, E. W. J. Am. Chem. Soc. 1945, 67, 2217–2218.
. As example of this behavior, the synthesis of 2,5-diethoxy-
carbonyl-3,4-ethylendioxythiophene (5 R = –(CH ) –) in
We gratefully acknowledge financial support by the
DFG and the Fonds der Chemischen Industrie (Ger-
many). B. A. Frontana thanks the DAAD (Germany)
for the exchange fellowship and the IACIC-IQ-UNAM
8
(
Mexico) for financial support. This paper is contribu-
2
2
tion No. 2634 from IQ-UNAM.
2
2
–
4 h reaction time has a 70% yield, the synthesis of
,5-diethoxycarbonyl-5-octyldioxeno[2,3-c]thiophene (5 R =
(CH CH(C H )–) in 48 h reaction time has a 52% yield
2
8
17
References and notes
. (a) Roncali, J. Chem. Rev. 1992, 92, 711–738; (b) M u¨ llen,
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xeno[2,3-c]thiophene (5 R = –(CH CH(C14 29)–) in 48 h
reaction time has 24% yield. See Ref. for details.
2
H
3
h
1
K.; Wegner, G. Electronic Materials: The oligomer
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12. For this compound the typical acid-catalyzed acetal
formation reactions using benzaldehyde, benzaldehyde
dimethyl acetal or p-anisaldehyde dimethyl acetal and 1 in
DMF or dry benzene or toluene also failed to produce
compound 5a. The acid catalysis must decrease the
nucleophilicity of 1, which by its nature is a poor
nucleophile, due to the stability of its conjugated base (1
1
3
. Use as antistatic coatings: (a) M u¨ ller, H.; Schultze, D.;
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syntheses of the 5 by the route depicted in Scheme 1 are
carried out in basic media or by the use of the
corresponding di-potassium salt 3.
ꢀ
13. It was confirmed that the dipotassium salt (3) of 1 reduces
rapidly the Ag(I) ion to Agꢁ in the basic conditions. This
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4
5
6
(
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. (a) Heywang, G.; Jonas, F. Adv. Mater. 1992, 4, 116–118;
(
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(
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