NEW ELECTRONꢀACCEPTING QUINOXALINOTHIADIAZOLEꢀCONTAINING ...
207
derivative 17 in 95% yield. Next, compound 17 was
acylated with oxalyl chloride in the presence of AlCl3
to give compound 18 as a viscous yellow oil in satisfacꢀ
tory yield of 44%. In the final stage, the condensation
ACKNOWLEDGMENTS
M. L. Keshtov, S. A. Kuklin, S. N. Osipov, and
S. M. Masoud are grateful to the Russian Science Founꢀ
dation for the financial support of the experimental and
spectral studies (project no. 14–13–01444).
of equimolar amount of intermediate ꢀdiketone 18
α
with diamine 10 resulted in target product 19 as a visꢀ
cous crimson oil in 58% yield after purification by colꢀ
umn chromatography.
REFERENCES
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. Heeger, A.J., Adv. Mater., 2014, vol. 26, pp. 10–28.
The composition and structure of intermediate
2. Zhan, X. and Zhu, D., Poly. Chem., 2010, vol. 1,
compounds 12–18 and target product 19 were conꢀ
pp. 409–419.
1
13
19
firmed by elemental analysis and H, C, and F
NMR. In particular, the 12H NMR spectrum of comꢀ
pound 19 displays a triplet of doublets, a doublet of
doublets, and one multiplet in the downfield region at
3
. Chen, Z., Cai, P., Chen, J., Liu, X., Zhang, L., Lan, L.,
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(
8
1
δ
, ppm) 6.82 (td,
.0, 2.0 Hz, 2H), 7.85 (t, 6H), respectively, related to
0 aromatic protons. The upfield region contains a sigꢀ
= 1.88 ppm (t, = 8.19 Hz, 8H) from the eight
J = 9.4, 4.2 Hz, 2H), 6.90 (dd, J =
2014, vol. 7, pp. 2276–2284.
5. Cheng, Y.ꢀJ., Yang, S.ꢀH., and Hsu, C.ꢀS., Chem. Rev.,
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nal at
δ
J
6. Keshtov, M.L., Kuklin, S.A., Chen, F.C., Khokhlov, A.R.,
Kurchania, R., and Sharma, G.D., J. Polym. Sci., Part
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Ostapov, I.E., Godovsky, D.Yu., and Khokhlov, A.R.,
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. Keshtov, M.L., Marochkin, D.V., Kochurov, V.S.,
Khokhlov, A.R., Koukarascd, E.N., and Sharma, G.D.,
Polym. Chem., 2013, vol. 4, pp. 4033–4044.
protons of the methylene groups directly adjacent to
the fluorene moieties, while the signals that belong to
the other 92 protons of the alkyl substituents appear in
the range 1.40–0.60 ppm (Fig. 2a). The C NMR
spectrum of compound 19 in the range 110–170 ppm
exhibits 11 signals that belong to 11 different quaterꢀ
nary aromatic carbon atoms, the signals of C5, C3,
and C6 atoms being doublets of doublets with spin–
spin coupling constants JC–F = 250.1, 11.0; 254.9,
7
8
9
13
. Wienk, M.M., Turbiez, M., Gilot, J., and Janssen, R.A.J.,
Adv. Mater., 2008, vol. 20, pp. 2556–2560.
1
3.3; 8.5, 6.1; and 14.6, 2.4 Hz, respectively. The sigꢀ
1
0. Zou, Y., Najari, A., and Berrouard, P., Beaupré, S.,
Réda, A.B., Tao, Y., and Leclerc, M., J. Am. Chem.
Soc., 2010, vol. 132, pp. 5330–5331.
1. Stalder, R., Mei, J., and Reynolds, J.R., Macromoleꢀ
cules, 2010, vol. 43, pp. 8348–8352.
nal from the C7 atom is a doublet with JC–F = 7.8 Hz.
Five signals related to five tertiary aromatic carbon
atoms are present within 110–130 ppm, the signals of
C2 and C4 atoms are doublets of doublets with JC–F
2
from C8 atom is a doublet with JC–F = 5.0 Hz. The
upfield region includes signals at 56.56 and 14.11 ppm
related to the carbon atom of the cyclopentadiene
moiety of fluorene and the terminal CH groups of the
alkyl substituents, respectively. The signals related to
1
=
1
2. Keshtov, M.L., Toppare, L., Marochkin, D.V.,
Kochurov, V.S., Parashchuk, D.Yu., Trukhanov, V.A.,
and Khokhlov, A.R., Vysokomol. Soedin., Ser. B, 2013,
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2.5, 3.2; and 24.6, 3.0 Hz, respectively. The signal
1
3. Keshtov, M.L., Kochurov, V.S., Sharma, G.D., and
Khokhlov, A.R., Vysokomol. Soedin., Ser. B, 2013,
vol. 55, no. 6, pp. 737–745.
3
other aliphatic carbon atoms are detected in the region 14. Liang, Y.Y., Feng, D.Q., Wu, Y., Tsai, S.T., Li, G., Ray,
C., and Yu, L.P., J. Am. Chem. Soc., 2009, vol. 131,
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4
1–22 ppm, which additionally confirms the proꢀ
19
posed structure (Fig. 2b). The F NMR spectra show
two signals at –109.56 and –115.08 ppm related to two
different fluorine atoms, which additionally confirms
the proposed structure of fluorinated monomer 19
1
,
2
(
Fig. 2c).
Translated by I. Kudryavtsev
DOKLADY CHEMISTRY Vol. 468
Part 2 2016