New 2,7-diiodo-9,9-disubstituted fluorene containing tetrathiafulvalene fragments

Full text of DOI:10.1134/S1070428006120244

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2006, Vol. 42, No. 12, pp. 1873–1876. © Pleiades Publishing, Inc., 2006.
Original Russian Text © G.G. Abashev, K.Yu. Lebedev, I.V. Osorgina, E.V. Shklyaeva, 2006, published in Zhurnal Organicheskoi Khimii, 2006, Vol. 42,
No. 12, pp. 1880–1882.
SHORT
COMMUNICATIONS
New 2,7-Diiodo-9,9-disubstituted Fluorene Containing
Tetrathiafulvalene Fragments
G. G. Abasheva,b, K. Yu. Lebedevc, I. V. Osorginab, and E. V. Shklyaevab
a Institute of Technical Chemistry, Ural Division, Russian Academy of Sciences, Perm, Russia
b Institute of Natural Sciences, ul. Genkelya 4, Perm, 614990 Russia
e-mail: gabashev@psu.ru
c Perm State University, Perm, Russia
Received December 12, 2005
DOI: 10.1134/S1070428006120244
cyclic halogen derivatives to be performed according
to Suzuki or Stille [6].
Over the past 30 years, tetrathiafulvalenes and their
derivatives attract researchers’ attention primary due to
electroconducting and superconducting properties of
radical cation salts derived therefrom [1]. On the other
hand, derivatives of fluorene and carbazole attract con-
tinuously increasing interest as fragments of organic
oligomers and polymers. These compounds possess
such unique properties as high thermal and chemical
stability and high luminescence quantum yield. There-
fore, they can be used as materials for the preparation
of organic light-emitting diodes (LEDs) [2, 3], field-
emitting transistors (FETs) [4], and full-color polymer-
ic display devices which are superior to liquid crystal
displays (LCDs). It seems to be promising to synthe-
size oligomers and polymers simultaneously contain-
ing both electrically active tetrathiafulvalene moieties
and substituted fluorene or carbaxole fragments and
examine their optical, electrochemical, and electro-
physical properties. In the recent years, fairly extensive
studies have been performed on conductive thiophene-
based polymers containing electrically active tetrathia-
fulvalene fragments (TTF) [5]. However, there are no
published data on polymers derived from other TTF-
containing heterocyclic monomers.
Compound VI was synthesized in four steps.
Fluorenone I was halogenated with iodine in a mixture
of acetic acid with carbon tetrachloride in the presence
of nitric and sulfuric acids [7]; 2,7-diiodofluoren-9-one
(II) thus obtained reacted with phenol in carbon tetra-
chloride in the presence of methanesulfonic acid [8] to
give 9,9-bis(4-hydroxyphenyl) derivative III which
was alkylated with 1,6-dibromohexane in acetone in
alkaline medium (in a solution of potassium hydroxide
in methanol). Substituted fluorene IV having reactive
bromine atoms was then used as alkylating agent in the
reaction with 2 equiv of cesium thiolate Vb; the latter
was prepared in turn by reaction of tetrathiafulvalene
Va with 1 equiv of CsOH·H2O in DMF (Scheme 1).
Tetrathiafulvalene Va [9] was synthesized by cross-
coupling of 4-(2-cyanoethylsulfanyl)-5-methylsul-
fanyl-1,3-dithiol-2-one (VII) [9] with 4,5-ethylenedi-
sulfanyl-1,3-dithiole-2-thione (VIII) [10] (Scheme 2).
Initial heterocyclic compounds VII and VIII were pre-
pared by alkylation of zinc dithiolate complex IX with
the corresponding alkyl halides (compound IX was
obtained by reaction of carbon disulfide with metallic
sodium in DMF [11]). 4,5-Bis(2-cyanoethylsulfanyl)-
1,3-dithiol-2-thione (X) was converted into 4-(2-cyano-
ethylsulfanyl)-4-methylsulfanyl-1,3-dithiole-2-thione
(XI) by successive treatment with 1 equiv of CsOH·
H2O and MeI [9, 12]. Heterocyclic compound XI was
heated in AcOH in the presence of Hg(OAc)2 to obtain
oxygen derivative VII that was directly involved in the
cross coupling to synthesize Va. This reaction was
We have synthesized substituted fluorene VI which
is a complex molecular assembly including a fluorene
system and two benzene rings attached to C9 of the
fluorene fragment and linked to tetrathiafulvalene moi-
eties through eight-membered hydrocarbon bridges.
Molecule VI contains two iodine atoms in positions 2
and 7, which enable polymerization of this compound
or its copolymerization with other aromatic or hetero-
1873

ABASHEV et al.
1874
Scheme 1.
I
I
I
OH
OH
O(CH2)6Br
a
b
c
O
O
O(CH2)6Br
I
I
I
I
II
III
IV
SMe
S
SMe
S
S
S
S
S
S
S
S
S
S
S
S
d
Cs+
S
CN
Va
Vb
MeS
S
S
S
S
S
S
I
S
O
O
e
IV
+
Vb
S
S
S
S
S
S
S
I
MeS
VI
a: I2, AcOH–CCl4, HNO3–H2SO4; b: phenol, MeSO3H, CCl4; c: 1,6-dibromohexane, KOH, MeOH, Me2CO; d: DMF, CsOH·H2O–
MeOH; e: 10 h, reflux.
accompanied by formation of two symmetric tetrathia-
fulvalenes as a result of self-coupling of 1,3-dithiol-2-
one VII and 1,3-dithiole-2-thione VIII. The target
cross-coupling product, tetrathiafulvalene Va, was iso-
lated by either fractional crystallization from acetoni-
trile or column chromatography (eluent ethyl acetate–
hexane, 1:2).
off, washed with water until neutral washings, dried in
air, and recrystallized from ethyl acetate or toluene–
acetic acid (1:1). Yield 75%, yellow needles, mp 205–
206°C. IR spectrum (mineral oil): ν(C=O) 1715 cm–1.
1H NMR spectrum, δ, ppm: 7.16 d and 7.18 d (1H
each), 7.73 d and 7.76 d (1H each), 7.85 s (2H).
9,9-Bis(4-hydroxyphenyl)-2,7-diiodo-9H-fluor-
ene (III). A mixture of 1.8 g (0.01 mol) of fluorenone
II, 6.27 g (0.067 mol) of phenol, and 2.85 g (0.03 mol)
of methanesulfonic acid in 20 ml of CCl4 was heated
for 40 h at 80°C under stirring. The solvent was dis-
tilled off to 1/5 of the initial volume, and the product
was purified by repeated reprecipitation from acetone
with water. Yield 55%, colorless crystalline substance,
2,7-Diiodo-9H-fluoren-9-one (II). A solution of
4.5 g (0.025 mol) of fluorenone I and 6.35 g
(0.025 mol) of molecular iodine in a mixture of 50 ml
of glacial acetic acid and 3 ml of carbon tetrachloride
(to wash off sublimed iodine) was heated to the boiling
point, a mixture of 1 ml of concentrated sulfuric acid
and 2 ml of fuming nitric acid was added dropwise,
and the mixture was heated for 3.5 h under reflux.
Some time after the addition of the acid mixture, a yel-
low solid separated from the reaction mixture. The
mixture was cooled, and the precipitate was filtered
1
mp 240°C. H NMR spectrum, δ, ppm: 6.66 d.d and
6.63 d.d (2H each), 6.92 d.d and 6.95 d.d (2H each),
7.37 d and 7.40 d (1H each), 7.58 d and 7.59 d (1H
each), 7.60 d and 7.61 d (1H each).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 12 2006

NEW 2,7-DIIODO-9,9-DISUBSTITUTED FLUORENE
1875
Scheme 2.
S
S
a
S
S
S
S
S
S
S
S
S
S
S
VIII
Zn
S
S
[NEt4]2
S
S
S
S
S
S
b
c
NC
NC
Me
IX
S
S
NC
S
S
X
XI
S
S
d
Me
O
NC
NC
S
S
VII
SMe
SMe
S
S
S
S
S
S
S
S
S
e
VII
+
VIII
+
S
S
S
CN
CN
MeS
S
Va
S
S
S
S
S
S
S
S
+
a: BrCH2CH2Br, Me2CO, Δ, 4–5 h; b: BrCH2CH2CN, Me2CO, Δ, 3–4 h; c: (1) CsOH·H2O–MeOH, DMF; (2) MeI;
d: Hg(OAc)2–AcOH, Δ; e: P(OEt)3.
9,9-Bis[4-(6-bromohexyloxy)phenyl]-2,7-diiodo-
0.13 g (0.78 mmol) of CsOH·H2O in 5 ml of anhy-
drous methanol was added in one portion, the mixture
was stirred for 30 min, a solution of 0.36 g
(0.39 mmol) of fluorene IV in 5 ml of DMF was ad-
ded, and the mixture was heated for 10 h under reflux.
It was then cooled and diluted with water, and the pre-
cipitate was filtered off, washed with a large amount of
water, dried in air, and purified by chromatography on
silica gel using ethyl acetate–hexane (1:2) as eluent.
Yield 42%, red crystalline substance, mp 72–73°C.
1H NMR spectrum, δ, ppm: 1.37 m and 1.4 m (12H),
1.52 m and 1.67 m (4H), 2.38 s (6H), 2.74 t (4H),
3.21 d and 3.22 d (4H each), 3.84 t (4H), 6.63 d.d and
6.71 d.d (2H each), 6.95 t (4H), 7.37 d and 7.39 d
(1H each), 7.58 d and 7.61 d (2H each). Found, %:
I 16.93; S 34.12. C55H52I2O2S15. Calculated, %:
I 16.79; S 33.93.
9H-fluorene (IV). Compound III, 2 g (3.3 mmol), was
added to a solution of 0.37 g (6.6 mmol) of potassium
hydroxide in 15 ml of methanol, and the resulting dark
red solution of bis-phenoxide was added dropwise to
a solution of 2.44 g (0.01 mol) of 1,6-dibromohexane
in 15 ml of acetone. The mixture was heated until the
red color disappeared, cooled, diluted with water, and
extracted with diethyl ether. The extract was dried over
Na2SO4, the solvent was removed under reduced
pressure, and the residue was washed with hexane to
remove excess 1,6-dibromohexane. The product was
brought into further transformations without additional
purification. Yield 73%, red viscous oily substance.
1H NMR spectrum, δ, ppm: 1.32 m and 1.33 m (12H),
1.63 m and 1.73 m (4H), 3.27 t (4H), 3.76 t (4H),
6.57 d.d and 6.66 d.d (2H each), 6.89 d.d and 6.97 d.d
(2H each), 7.29 d and 7.31 d (1H each), 7.50 d and
7.53 d (1H each), 7.58 s (2H).
1
The H NMR spectra were recorded on a Mercury
Plus-300 spectrometer using hexamethyldisiloxane as
internal reference. The IR spectra were measured on
a UR-20 spectrometer.
2,7-Diiodo-9,9-bis(4-{6-[5-methylsulfanyl-2-(4,5-
ethylenedisulfanyl-1,3-dithiol-2-ylidene)-1,3-dithiol-
4-ylsulfanyl]hexyloxy}phenyl)-9H-fluorene (VI).
Tetrathiafulvalene Va, 0.33 g (0.78 mmol), was dis-
solved in 10 ml of anhydrous DMF (preliminary
purged with argon) on slight heating, a solution of
This study was performed under financial support
by the Russian Foundation for Basic Research (project
nos. 04-03-96036, 05-03-32849a).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 12 2006

ABASHEV et al.
5. Huchet, L., Akoudad, S., and Roncali, J., Adv. Mater.,
1876
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