1818
B. Rungtaweevoranit et al. / Tetrahedron Letters 53 (2012) 1816–1818
Acknowledgments
HO
OH
OH
HS
S
Ar
H+
Financial support from the National Synchrotron Research
Ar
Center (Grant 2-2549/PS01), the Royal Golden Jubilee (RGJ)
program, the Development and Promotion of Science and Technol-
ogy Talents (DPST), the Center of Excellence for Innovation in
Chemistry (PERCH-CIC) and the Thailand Graduate Institute of
Science and Technology (TGIST) are gratefully acknowledged.
22
25
23
-H2O
H
-H+
S
S
Ar
Ar
Supplementary data
24
Supplementary data associated with this article can be found, in
Scheme 3. The proposed mechanism for the formation of dihydrothiophene
derivatives.
References and notes
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aromaticityof thebenzene ring. This procedure couldalso be applied
to pyren-1-ol (7) to provide 14 in a 42% yield.
Subsequently, oxidation of the hydrothiophenes 8–14 with
chloranil gave thiophene derivatives 15–21 in moderate to good
yields.
A mechanism for dihydrothiophene formation can be proposed
as follows. Nucleophilic aromatic substitution of hydroxyarene 22
takes place via keto-enol tautomerization of a hydroxyarene
followed by the attack of the more nucleophilic sulfur to form a
hemithioacetal which undergoes rearomatization.14a,19 Subse-
quent intramolecular Friedel–Crafts type cyclization and rearoma-
tization provided the dihydrothiophene 25 via intermediate 24
(Scheme 3).20
In summary, a synthetic strategy for the introduction of thio-
phene as end caps on aromatic systems has been established.
The advantage of this method is the straightforward and efficient
experimental methodology together with the ready availability of
the starting materials. The method could be applied for the prepa-
ration of a variety of thiophene derivatives allowing a convenient
access to naphthothiophenes, naphthodithiophenes, and terthieno-
benzene. This finding could accelerate the discovery of new
applications in thiophene-based organic electronic devices.
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Typical procedure for the synthesis of dihydrothiophene
derivatives
Preedasuriyachai,
P.;
Charoonniyomporn,
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Karoonnirun,
O.;
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Nakazawa, T.; Hirose, N.; Itabashi, K. Synthesis 1989, 955.
Dihydrothiophene derivative 8
2-Mercaptoethanol (1.46 ml, 20.80 mmol) was added to
a
stirred solution of 2-naphthol (1) (0.50 g, 3.47 mmol) in chloro-
benzene (15 mL). Next, TfOH (0.77 ml, 8.67 mmol) was added
slowly at room temperature and the mixture was heated at reflux
for 3 h. (It should be noted that a white solid started to form in
the solution which gradually dissolved during heating.) The
mixture was cooled to room temperature and quenched with
5% NaOH solution (50 mL), followed by extraction with CH2Cl2
(2 Â 40 ml). The organic extract was dried over Na2SO4, filtered,
and evaporated to dryness. The crude residue was purified by
column chromatography to provide compound 8 (0.34 g, 52%
yield) as a white solid.
16. (a) Lienhard, G. E.; Jencks, W. P. J. Am. Chem. Soc. 1966, 88, 3982; (b) Sander, E.
G.; Jencks, W. P. J. Am. Chem. Soc. 1968, 90, 6154.
17. It is postulated that excess H2O present in the reaction mixture might facilitate
the formation of the unidentified solid by-product and thus should be avoided.
18. (a) Trace amounts of oxidized products were observed in the synthesis of
compounds 8 and 9. (b) Reaction between 2,3-dihydroxynaphthalene (3) and
1,2-ethanedithiol in the presence of TfOH provided 2,3-dihydronaphtho[2,
3-b][1,4]dithiine. A similar transformation has been observed, see Ref. 14b.
19. Jacobsson, M.; Oxgaard, J.; Abrahamsson, C.-O.; Norrby, P.-O.; Goddard, W. A.;
Ellervik, U. Chem. Eur. J. 2008, 14, 3954.
20. For another possible mechanism, see Ref. 10.