Novel crown-containing 3-styryl derivatives of oligothiophenes: Synthesis, structure, and optical and electrochemical characteristics

Article abstract of DOI:10.1007/s11172-009-0203-3

A method for the synthesis of the 3-substituted polythiophene derivatives including two crown-containing styryl fragments was proposed. The optical properties of the obtained compounds are characterized by the presence of intense absorption and fluorescence bands. The oxidation to the thiophene derivatives involves the crown-containing styryl fragment and should be sensitive to the presence of the metal cation in the crown ether cavity.

Full text of DOI:10.1007/s11172-009-0203-3

Russian Chemical Bulletin, International Edition, Vol. 58, No. 7, pp. 1509—1515, July, 2009
1509
Novel crownꢀcontaining 3ꢀstyryl derivatives of oligothiophenes:
synthesis, structure, and optical and electrochemical characteristics
E. V. Lukovskaya,a A. A. Bobyleva,a O. A. Fedorova,a Yu. V. Fedorov,b
A. V. Anisimov,a Y. Didane,c H. Brisset,c and F. Fagesc
aDepartment of Chemistry, M. V. Lomonosov Moscow State University,
1/3 Leninskie Gory, 119992 Moscow, Russian Federation.
Eꢀmail: lukov@petrol.chem.msu.ru
bA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 ul. Vavilova, 119991 Moscow, Russian Federation
cFaculte des Sciences de Luminy, Universite de la Mediterranee,
UMR 6114 CNRS, Marseille, 13288 France
A method for the synthesis of the 3ꢀsubstituted polythiophene derivatives including two
crownꢀcontaining styryl fragments was proposed. The optical properties of the obtained comꢀ
pounds are characterized by the presence of intense absorption and fluorescence bands. The
oxidation to the thiophene derivatives involves the crownꢀcontaining styryl fragment and should
be sensitive to the presence of the metal cation in the crown ether cavity.
Key words: thiophenes, polythiophenes, benzoꢀ15ꢀcrownꢀ5 ethers, crossꢀcoupling, 1H and
13С NMR spectra, absorption spectra, fluorescence spectra, electrochemistry.
The intensive development of chemistry of polyꢀ
thiophenes is associated with their electronic and optical
properties, which makes it possible to use these compounds
for the creation of efficient field transistors,1,2 organic laꢀ
ser diodes,3 cells of solar batteries,4 and electroluminesꢀ
cence devices.5
Specific functionalization of conducting thiophene
polymers is important for the development of chemical
sensors with high sensitivity and stability.6—8 In particuꢀ
lar, crown ethers with ionophoric properties and covalentꢀ
ly linked with polythiophenes undergo complex formation
reactions with metal ions to change considerably the optiꢀ
cal and electrochemical characteristics of the whole sysꢀ
tem, thus providing these compounds with the properties
of efficient sensors.
We have earlier20,21 reported the synthesis and properꢀ
ties of new crownꢀcontaining bis(2ꢀstyryl)polythiophenes.
The compounds demonstrated the properties of optical
and electrochemical sensors for alkalineꢀearth metal catꢀ
ions. A distinctive feature of the compounds is their ability
to intermolecular sandwich organization in the presence
of cations with larger sizes and in monolayers. The formaꢀ
tion of intermolecular aggregates considerably decreased
the intensity of the absorption and fluorescence spectra of
the molecules and increased their electrochemical activiꢀ
ty. In the present work, we developed methods for the
synthesis of earlier unknown crownꢀcontaining 3ꢀstyrylꢀ
Crownꢀcontaining polythiophenes were first obtained9
in 1993, when the starting monomers represented bisꢀ
thiophenes linked at positions 3,3´ by the polyether chain.
Crownꢀannelated polythiophenes were studied,10—13 and
azaꢀ and oxathiacrown ethers containing three thiophene
fragments were obtained.14,15 Oligothiophenes linked with
the crown ether fragment through the spacer were syntheꢀ
sized.16—19 The influence of complex formation of the
thiopheneꢀcontaining crown ethers on their optical and
electrochemical characteristics was described only in sevꢀ
eral works9,10,12,13,15 for several cations (Na, K, Ba, Sr, Pb)
and, therefore, studies in this direction are significant for
the development of new efficient receptors.
n = 0, R = H; n = 1,2, R =
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1465—1470, July, 2009.
1066ꢀ5285/09/5807ꢀ1509 © 2009 Springer Science+Business Media, Inc.

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Lukovskaya et al.
substituted monoꢀ, triꢀ, and tetrathiophenes and deterꢀ
mined their optical and electrochemical characteristics.
The structure of the compounds does not favor the interꢀ
molecular organization, which makes it possible to obtain
systems substantially different by the optical and electroꢀ
chemical responses from the earlier studied isomeric
crownꢀcontaining 2ꢀstyrylthiophenes.
In the compounds presented two oxygen atoms of the
macrocycle are conjugated with the benzene ring of benꢀ
zocrown ether upon the complex formation of the latter
with the metal cations that involves these heteroatoms.
Due to this, the electron density distribution changes in
the molecules, changing the spectral and electrochemical
characteristics of the whole system. A more stable electroꢀ
chemical response can be expected with an increase in the
number of thiophene fragments responsible for the elecꢀ
trochemical characteristics.
Unlike the earlier studied crownꢀcontaining 2ꢀstyrylꢀ
substituted oligothiophenes,20 in the isomeric 3ꢀsubstitutꢀ
ed compounds the vinylbenzocrown ether substituents will
create certain steric hindrances, which may change torꢀ
sion angles between the thiophene fragments and affect
the degree of conjugation in the whole system, complex
formation, and optical and electrochemical properties.
1 : 3 gave a poorly soluble mixture of products, and an
increase in the amount of NBS resulted in the predomiꢀ
nant formation of a mixture of tribromides. In the absence
of benzoyl peroxide, the bromination also proceeded to
both the lateral chain and cycle. The addition of a catalytꢀ
ic amount of HClO4 to the reaction mixture for the elecꢀ
trophilic bromination of 3ꢀmethylthiophene according to
Ref. 23 at the substrate to NBS ratio equal to 1 : 2 gave
2,5ꢀdibromoꢀ3ꢀmethylthiophene, while at the equimolar
amounts of the reactants 2ꢀbromoꢀ3ꢀmethylthiophene 1
was formed (Scheme 1).
The latter was selectively brominated with NBS in the
presence of benzoyl peroxide to target dibromide 2а.
3ꢀMethylthiophene was selectively brominated only to the
lateral chain with the formation of compound 2b using
2,2´ꢀazobisisobutyronitrile (AIBN) as the initiator of the
radical reaction. Then bromides 2a,b were transformed
into diethyl phosphonates 3a,b, which were condenꢀ
sed with 4ꢀformylbenzoꢀ15ꢀcrownꢀ5 in the presence of
50% NaOH and Aliquat 336 (methyltrioctylammonium
chloride) to form 15[(E)ꢀ2ꢀ(2ꢀbromoꢀ3ꢀthienyl)vinyl]ꢀ
2,3,5,6,8,9,11,12ꢀoctahydroꢀ1,4,7,10,13ꢀbenzopentaoxaꢀ
cyclopentadecane (4a) and 15ꢀ[(E)ꢀ2ꢀ(3ꢀthienyl)vinyl]ꢀ
2,3,5,6,8,9,11,12ꢀoctahydroꢀ1,4,7,10,13ꢀbenzopentaoxaꢀ
cyclopentadecane (4b) in 48 and 42%, respectively. Based
on the spinꢀspin coupling constant (SSCC) values equal
to 16.4 and 15.9 Hz, we concluded the formation of crown
ethers 4a and 4b as Еꢀisomers. Then compound 4a was
used for the synthesis of crownꢀcontaining oligothiophenes
(Scheme 2).
Results and Discussion
The general strategy of the synthesis of the target comꢀ
pounds corresponded that described earlier.20 3ꢀMethylꢀ
thiophene was used as one of the starting components.
An attempt of the direct bromination of 3ꢀmethylꢀ
thiophene with NBS in benzoyl peroxide by a known methꢀ
od22 at the substrate to NBS mole ratio equal to 1 : 2 and
Polythiophenes 5 and 6 bearing three and four thioꢀ
phene fragments were synthesized according to the Stille
method24 in the presence of Pd[PPh3]4 in 64 and 79%
Scheme 1
R = Br (a), H (b)

Crownꢀcontaining polythiophene systems
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 7, July, 2009
1511
Scheme 2
yields, respectively. 2,5ꢀBis[tri(nꢀbutyl)stannyl]thiophene
and 5,5´ꢀbis[tri(nꢀbutyl)stannyl]ꢀ2,2´ꢀbithiophene (7 and 8)
were synthesized according to a described procedure.25
The structures of all synthesized compounds were
proved using 1H and 13С NMR spectroscopy, mass specꢀ
trometry, and UV spectroscopy and confirmed by eleꢀ
mental analysis data.
As can be seen from the 1Н NMR spectrum (CD3CN +
+ CDCl3) (Fig. 1), compound 5 is highly symmetric and,
therefore, its spectrum is presented by signals of one crownꢀ
containing styryl fragment and two thiophene heterocycles.
The signals of protons of the central third thiophene
ring in compound 5 have the same chemical shift
(7.22 ppm) and represent an intense singlet. Note that
signals of protons of the macrocycles of compounds 4b, 5,
and 6 have the same chemical shifts and multiplicity and
the variation of the number of thiophene fragments in the
molecules does not affect the NMR spectra of the macroꢀ
cyclic part.
tured band at 290—330 nm. The absorption spectrum of
compound 5 contains a band at 330 nm and a shoulder at
385 nm, whereas that of compound 6 exhibits a band at
413 nm and a structured band with a maximum at 325 nm.
The main structural difference between compounds 4b, 5,
and 6 is the length of the polythiophene chain. A comparꢀ
ison of the values of the absorption band maxima for comꢀ
pounds 4b, 5, and 6 shows that the position of the shortꢀ
wavelength absorption band remains virtually unchanged
on going from compound 4b to 5. At the same time, the
longꢀwavelength absorption band exists only in the specꢀ
trum of bisstyryl derivative 6 and is manifested as a shoulꢀ
der for derivative 5 (Fig. 2).
As shown by our calculations, in compound 4b both
the HOMO (highest occupied molecular orbital) and
LUMO (lowest unoccupied molecular orbital) are uniꢀ
formly delocalized over all fragments of the molecule, exꢀ
cept for the crown ethers, and it is most probable that the
HOMO—LUMO transition has the π,π*ꢀcharacter.26 In
compound 6 the HOMO is delocalized over all fragments
of the molecule, except for the crown ethers, whereas the
Optical characteristics of compounds 4b, 5, and 6. The
absorption spectrum of compound 4b has a broad strucꢀ
H(5, 6, 8, 9)
3.66
H(3″, 4″)
7.22
CH=CH, H(14, 16)
7.03
CH=CH, H(2´, 3´)
7.33
7.38
7.40
H(3, 11)
H(2, 12)
4.06
7.31
7.00
H(17)
6.80
3.81
3.78
7.30
6.78
7.40
7.30
7.20
7.10 7.00
6.90 6.80
4.00
3.75
δ
5
Fig. 1. 1H NMR spectrum of compound 5 in CD3CN + CDCl3 (1 : 1); the concentration of compound 5 is 5•10–4 mol L–1, 25 °C.

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Russ.Chem.Bull., Int.Ed., Vol. 58, No. 7, July, 2009
Lukovskaya et al.
A
Ifl(arb. units)
The fluorescence spectra of the polythiophene crownꢀ
containing derivatives in acetonitrile are also shown in
Fig. 2. The fluorescence spectrum of monostyryl derivaꢀ
1´
3´
1.0
0.8
0.6
0.4
0.2
0
2´
1.0
0.8
0.6
0.4
0.2
0
2
tive 4b has a relatively small Stokes shift of ∼3900 cm–1
,
whereas the fluorescence spectra of compounds 5 and 6
demonstrate a considerable bathochromic shift relative to
the absorption spectra, their Stokes shifts being 5900 and
4800 cm–1, respectively. The emission bands of comꢀ
pounds 4b, 5, and 6 are broadened and have a weakly
pronounced vibrational structure, which is characteristic
of polythiophenes.27
Electrochemical characteristics of compounds 4b, 5, and
6. The potential values for the oxidation and halfꢀwave of
the studied compounds are listed in Table 1.
3
1
200
300
400
500
600
λ/nm
Fig. 2. Electronic absorption (1—3) and fluorescence emission
(1´—3´) spectra of compounds 4b, 5, and 6 in MeCN; the conꢀ
centration of compounds 4b, 5, and 6 is 2•10–5 mol L–1, the
optical path length is 10 mm, and the excitation wavelength,
λ/nm: 300 (4b), 366 (5), and 425 (6).
The anodic process was found to be irreversible for
compounds 4b and 5. This phenomenon is very characterꢀ
istic of 3ꢀsubstituted thiophenes, because oxidation reꢀ
sults in electrodimerization on the electrode. The first
anodic potentials of oxidation for compounds 4b, 5,
and 6 are close, indicating that the oxidation occurs
in the styrylthiophene fragment and does not involve
the polythiophene chain. The radical cations of comꢀ
pounds 4b and 5 obtained at the first stage evidently
undergo electropolymerization.28 The oxidation of comꢀ
pound 6 is reversible and, hence, no compound 6 is obꢀ
LUMO is mainly localized on the thiophene fragments.
Therefore, it can be considered that the longꢀwavelength
absorption band in the spectrum of compound 6 is caused
by the intramolecular charge transfer from the donor to
acceptor part of the molecule (Fig. 3).
4b, LUMO
4b, HOMO
6, HOMO
Fig. 3. General view of the HOMO and LUMO for compounds 4b and 6.
6, LUMO

Crownꢀcontaining polythiophene systems
Russ.Chem.Bull., Int.Ed., Vol. 58, No. 7, July, 2009
1513
Table 1. Electrochemical characteristics (potentials
of the oxidation peaks Eoxpa/Epc and halfꢀwave E1/2
of compounds 4b, 5, and 6 according to the CV data)
the threeꢀelectron scheme. A platinum disk 1.6 mm in diameter
was used as the working electrode, and Ag/AgCl with a 3М solution
of NaCl and a platinum electrode served as the reference and
auxiliary electrodes, respectively. Tetrabutylammonium perchloꢀ
rate (Fluka) was used without additional purification. In meaꢀ
surements the concentrations of tetrabutylammonium perchlorꢀ
ate and the compound under study were 1 mol L–1. The solvent
Compound
Eoxpa/Epc
E1/2
V
was MeCN/CH2Cl2. The potential sweep rate was 250 mV s–1
.
4b
5
0.99*
0.96*
—
All reagents and solvents (Acros, Aldrich, Merck) of 99%
purity were used without additional purification.
1.10*
—
2ꢀBromoꢀ3ꢀmethylthiophene (1). 3ꢀMethylthiophene (7 g,
71 mmol) was added dropwise for 5 min to a suspension of reꢀ
crystallized NBS (12.7 g, 71 mmol) in CCl4 (70 mL), then 70%
HClO4 (0.1 g) was added, and the mixture was stirred at ambient
temperature for 18 h. After this К2СО3 (0.03 g) was added, the
reaction mixture was stirred for 10 min and filtered, the solvent
was distilled off in vacuo, and the residue was distilled. The
yield of bromide 1 was 9.9 g (79%), b.p. 74—77 °С (20 Torr),
nD20 1.5746 (cf. Ref. 21: b.p. 27 °С (1.8 Torr), nD20 1.5714).
2ꢀBromoꢀ3ꢀbromomethylthiophene (2a). A solution of broꢀ
mide 1 (9.9 g, 56 mmol) in CCl4 (30 mL) was added dropwise for
3 min to a suspension of NBS (10 g, 56 mmol) and benzoyl
peroxide (0.1 g, 0.4 mmol). The mixture was refluxed with stirꢀ
ring for 8 h and then filtered. The solvent was distilled off, and
the residue was distilled in vacuo. The yield of dibromide 2a was
6
0.93/0.89
0.91
* Irreversible process.
served in the extended conjugated system of electropoꢀ
lymerization.
Thus, the method for the synthesis of 3ꢀsubstituted
polythiophene derivatives bearing two crownꢀcontaining
styryl fragments is described in the present work. The opꢀ
tical properties of the synthesized compounds are shown
to be characterized by intense absorption and fluorescence
bands. The arrangement and shape of the bands depend
on the polythiophene structure. The optical properties of
the polythiophene derivatives are particularly determined
by the electronic transitions involving the oxygen atoms
of the crown ether fragments. This means that the comꢀ
plex formation with metal cations at the crown ether
fragments should be accompanied by changes in the optiꢀ
cal characteristics. The oxidation of the thiophene derivaꢀ
tives involves the crownꢀcontaining styryl fragment and
should be sensitive to the presence of the metal cation in
the crown ether cavity. Therefore, the compounds syntheꢀ
sized are potential optical and electrochemical receptors
of metal cations.
20
10.9 g (76%), b.p. 84—86 °С (3 Torr), nD 1.6358 (cf. Ref. 22:
b.p. 78 °С (2 Torr), nD20 1.6363).
3ꢀBromomethylthiophene (2b). A suspension of 3ꢀmethylꢀ
thiophene (20 g, 0.2 mol), NBS (35.6 g, 0.2 mol), and 2,2´ꢀbisꢀ
azoisobutyronitrile (0.4 g, 0.002 mol) in CCl4 (150 mL) was
carefully heated to boiling and refluxed for 2 h. The precipitate
was filtered off, the solvent was distilled, and the residue was
distilled off, and bromide 2b was obtained in a yield of 19.5 g
20
(57%), b.p. 86—90 °С (17 Torr), nD 1.5960, (cf. Ref. 22: b.p.
20
50 °C (1.5 Torr), nD 1.6035). 1Н NMR (CDCl3), δ: 4.50
(s, 2 H, CH2Br); 7.11 (dd, 1 H, H(4), J = 5.0 Hz, J = 1.2 Hz);
7.28 (m, 2 H, H(2), H(5)).
Diethyl 2ꢀbromoꢀ3ꢀthienylmethyl phosphonate (3a). Triethyl
phosphite (4.7 g, 28 mmol) and dibromide 2a (7.4 g, 29 mmol)
were heated at 100 °С and stirred in a flask equipped with the
short Liebig reflux condenser for 2 h. Ethyl bromide vapors were
collected in a cooled trap. The distillation of the reaction mixꢀ
ture gave phosphonate 3a (2.7 g, 30.4%), b.p. 180 °C (13 Torr).
Found (%): С, 34.48; Н, 4.49. С9H14BrO3PS. Calculated (%):
С, 34.52; Н, 4.54. 1Н NMR (CDCl3), δ: 1.26 (t, 6 H, CH3, J =
= 7.1 Hz); 3.15 (d, 2 H, CH2P; J = 21.2 Hz); 4.04 (q, 4 H,
CH2CH3, J = 7.1 Hz); 7.02 (d, 1 H, H of thiophene, J = 5.6 Hz);
7.22 (d, 1 H, H of thiophene, J = 5.6 Hz).
Diethyl 3ꢀthienylmethyl phosphonate (3b). Triethyl phosphite
(2.0 g, 12 mmol) and bromide 2b (2.1 g, 12 mmol) were heated at
100 °С and stirred in a flask equipped with a short Liebig reflux
condenser for 2 h. Ethyl bromide vapors were collected in
a cooled trap. The reaction mixture was distilled and phosphonꢀ
ate 3b was isolated in a yield of 1.9 g (66%), b.p. 137—140 °C
(3 Torr), nD20 1.4970. Found (%): С, 45.92; Н, 6.41. С9H15O3PS.
Calculated (%): С, 46.15; Н, 6.45. 1Н NMR (CDCl3), δ: 1.24
(t, 6 H, CH2CH3, J = 7.1 Hz), 3.18 (d, 2 H, CH2P, J = 20.4 Hz);
4.02 (q, 4 H, CH2CH3,, J = 7.2 Hz); 7.05 (d, 1 H, Н(4), J = 5.5 Hz);
7.14 (s, 1 H, Н(2)); 7.27 (d, 1 H, Н(5), J = 5.4 Hz).
Experimental
1
Н and 13С NMR spectra were recorded on a Bruker Avanceꢀ
400 spectrometer with working frequencies 400.13 and 100 MHz,
respectively, using CDCl3 and CD3CN as solvents and HMDS
as internal standard. Chemical shifts were measured with the
accuracy to 0.01 ppm, and SSCC were determined with the acꢀ
curacy to 0.1 Hz. Electronic absorption spectra were recorded
on VarianꢀCary and SpecordꢀM40 spectrophotometers atꢀ
tached to a computer. Fluorescence spectra were measured in
a FluroLog spectrofluorimeter (Jobin Yvon) at 20 1 °С.
Melting points were measured with a Melꢀtemp II instruꢀ
ment and were not corrected.
The reaction course and purity of isolated products were
monitored by TLC on Kieselgel 60 F254 plates (Merck). Column
chromatography was carried out on silica gel 0.060—0.200 mm
(Acros). Elemental analyses were performed at the Laboratory
of Organic Analysis of the Department of Chemistry of the M. V.
Lomonosov Moscow State University.
Cyclic voltammetry was carried out on a BAS 100 Potenꢀ
tiostat instrument (Bioanalytical Systems) with the BAS100W
Software (v. 2.3). The measurements were conducted via
15ꢀ[(E)ꢀ2ꢀ(2ꢀBromoꢀ3ꢀthienyl)vinyl]ꢀ2,3,5,6,8,9,11,12ꢀ
octahydroꢀ1,4,7,10,13ꢀbenzopentaoxacyclopentadecane (4a).

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Lukovskaya et al.
Phosphonate 3a (5.5 g, 18 mmol) and 4ꢀformylbenzoꢀ15ꢀcrownꢀ
5 (5.7 g, 20 mmol) in benzene (25 mL) were added to a mixture
of 50% NaOH (14 mL) and Aliquat 336 (1 g) in benzene (15 mL).
The reaction mixture was refluxed for 1 h and cooled. The orꢀ
ganic phase was separated, washed with water, and dried with
MgSO4. After benzene was evaporated, the obtained solid was
recrystallized from a petroleum ether—ethyl acetate (1 : 1) mixꢀ
ture. Crown ether 4a was obtained in a yield of 4.2 g (48%), m.p.
125—126 °С. Found (%): С, 52.56; Н, 5.07. С20H23BrO5S. Calꢀ
culated (%): С, 52.75; Н, 5.09. UV (MeCN), λmax/nm: 347.
1Н NMR (CDCl3), δ: 3.76 (s, 8 H, H(5), H(6), H(8), H(9));
3.92 (m, 4 H, H(3), H(11)); 4.17 (m, 4 H, H(2), H(12)); 6.84
(d, 1 H, H(17), J = 8.2 Hz); 6.88 (d, 1 H, CH=CH, J = 16.4 Hz);
6.93 (d, 1 H, CH=CH, J = 16.3 Hz), 7.04 (d, 1 H, H(16), J =
= 8.2 Hz); 7.05 (s, 1 H, H(14)); 7.17 (d, 1 H, J = 5.8 Hz), 7.24
(d, 1 H, J = 5.8 Hz). 13С NMR (CDCl3), δ: 68.73, 69.06, 69.34,
69.42, 70.26, 70.34 (C(3), C(5), C(6), C(8), C(9), C(11)); 70.88,
70.91 (C(2), C(12)); 110.38 (C(2´) of thiophene); 111.73, 113.59
(C(14), C(17)); 119.01, 120.37, 125.41, 125.88, 130.30 (C=C,
C(4´), C(5´) of thiophene, C(16)); 130.19 (C(15)), 138.14 (C(3´)
of thiophene); 149.05, 149.20 (C(13a), C(17a)).
15ꢀ[(E)ꢀ2ꢀ(3ꢀThienyl)vinyl]ꢀ2,3,5,6,8,9,11,12ꢀoctahydroꢀ
1,4,7,10,13ꢀbenzopentaoxacyclopentadecane (4b) was syntheꢀ
sized according to an analogous procedure from phosphonate 3b
(1.8 g) and 4ꢀformylbenzoꢀ15ꢀcrownꢀ5 (2.4 g). Crown ether 4b
was isolated in a yield of 1.2 g (42%), m.p. 142—144 °С.
Found (%): С, 63.75; Н, 6.39. С20H24O5S. Calculated (%):
С, 63.81; Н, 6.43. 1Н NMR (CDCl3), δ: 3.75 (s, 8 H, H(5), H(6),
H(8), H(9)); 3.91 (m, 4 H, H(3), H(11)); 4.15 (m, 4 H, H(2),
H(12)); 6.82 (d, 1 H, H(17), J = 7.8 Hz); 6.85 (d, 1 H, (CH=CH),
J = 15.9 Hz); 6.96 (d, 1 H, CH=CH, J = 15.7 Hz); 6.98 (d, 1 H,
H(16), J = 7.8 Hz); 7.00 (s, 1 H, H(14)); 7.19 (s, 1 H, H of
thiophene); 7.29 (m, 2 H, H of thiophene). 13С NMR (CDCl3),
δ: 69.13, 69.25, 69.63, 69.68, 70.56, 70.60, 71.13, 71.15 (C(2),
C(3), C(5), C(6), C(8), C(9), C(11), C(12)); 111.70, 114.10
(C(14),C(17)); 120.14, 121.31, 121.60, 124.88, 126.04, 128.41
(C=C, C(2´), C(4´), C(5´) of thiophene, C(16)); 131.06 (C(15));
140.24 (C(3´) of thiophene); 148.99, 149.29 (С(13a), C(17a)).
2,5ꢀBis(triꢀnꢀbutylstannyl)thiophene (7) and 5,5´ꢀbis(triꢀnꢀ
butylstannyl)ꢀ2,2´ꢀbithiophene (8) were synthesized according to
described procedures.25
3,3″ꢀBisꢀ(E)ꢀ[2ꢀ(2,3,5,6,8,9,11,12ꢀoctahydroꢀ1,4,7,10,13ꢀ
benzopentaoxacyclopentadecꢀ15ꢀyl)vinyl]ꢀ2,2´:5´,2″ꢀterthioꢀ
phene (5). A solution of stannylthiophene 7 (480 mg, 0.77 mmol)
and bromide 4a (700 mg, 154 mmol) in absolute DMF (25 mL)
was added in an argon atmosphere with Pd[PPh3]4 (8 mg,
0.007 mmol), and the mixture was stirred for 15 h at 90 °C.
A precipitate was formed in the reaction mixture. After evaporꢀ
ation of the main part of the solvent, the suspension formed was
filtered off, and the precipitate was washed with acetone and
ether and then dissolved in chloroform. The solution was washed
with water and dried with MgSO4. After the solvent was evaporꢀ
ated, target product 5 was obtained as yellow crystals, m.p.
108 °C. Found (%): С, 62.99; Н, 5.73. С44H48O10S3. Calculatꢀ
ed (%): С, 63.44; Н, 5.81. UV (MeCN), λmax/nm: 330, 390.
1Н NMR (CDCl3), δ: 3.74 (s, 16 H, H(5), H(6), H(8), H(9));
3.88 (m, 8 H, H(3), H(11)); 4.13 (m, 8 H, H(2), H(12)); 6.79
(d, 2 H, H(17), J = 8.2 Hz); 6.93 (d, 2 H, CH=CH, J = 16.1 Hz);
7.00 (s, 2 H, H(14)); 7.03 (d, 2 H, H(16), J = 8.4 Hz); 7.16 (s, 2 H,
H of thiophene); 7.22 (d, 2 H, H of thiophene, J = 5.1 Hz); 7.27
(d, 2 H, CH=CH, J = 16.1 of thiophene); 7.34 (d, 2 H, H of
thiophene, J = 5.4 Hz). 13С NMR (CDCl3), δ: 68.91, 69.08,
69.51, 69.51, 70.42, 70.46, 71.02, 71.02 (CH2О); 112.08, 113.88
(C(14), C(17)); 120.12 (C=C), 120.12 (16); 124.86, 126.26,
127.35 (C of thiophene); 130.17 (C=C); 130.87, 131.62, 136.25,
136.36 (C of thiophene, C (15)); 149.08, 149.15 (C(13a), C(17a)).
3,3´´´ ꢀBis(E)ꢀ[2ꢀ(2,3,5,6,8,9,11,12ꢀoctahydroꢀ1,4,7,10,13ꢀ
benzopentaoxacyclopentadecꢀ15ꢀyl)vinyl]ꢀ2,2´:5´,2´´ :5´´ ,2´´´ ꢀ
quaterthiophene (6). A solution of stannylthiophene 8 (410 mg,
0.55 mmol) and bromide 4a (500 mg, 1.1 mmol) in absolute
DMF (20 mL) under an argon atmosphere was added with
Pd[PPh3]4 (5.7 mg, 0.005 mmol), and the mixture was stirred for
12 h at 90 °C. After the main part of the solvent was evaporated,
the suspension formed was filtered, and the precipitate was
washed with acetone and ether. The remained precipitate was
dissolved in chloroform, washed with water, and dried with
MgSO4. After the solvent was evaporated, target product 6 was
obtained as red crystals, m.p. 208 °C. Found (%): C, 62.97;
H, 5.33. C48H50O10S4. Calculated (%): С, 63.00; Н, 5.51. UV
(MeCN), λmax/nm: 325, 413. 1Н NMR (CDCl3), δ: 3.74 (s, 16 H,
H(5), H(6), H(8), H(9)); 3.89 (m, 8 H, H(3), H(11)); 4.14
(m, 8 H, H(2), H(12)); 6.82 (d, 2 H, H(17), J = 7.9 Hz); 6.93
(d, 2 H, CH=CH, J = 16.1 Hz); 7.01 (s, 2 H, H(14); 7.03
(d, 2 H, H(16), J = 8.3 Hz); 7.07 (d, 2 H, H of thiophene,
J = 3.79 Hz); 7.17—7.23 (m, 4 H, H of thiophene); 7.22 (d, 2 H,
CH=CH, J = 16.1 Hz); 7.32 (d, 2 H, H of thiophene, J = 5.4 Hz).
13С NMR (CDCl3), δ: 68.97, 69.15, 69.53, 69.56, 70.44, 70.49,
71.04, 71.04; 112.15, 113.93 (C(14), C(17)); 120.18 (4 C, C=C,
C(16)); 124.39, 124.88, 126.30, 127.57 (C of thiophene); 130.19
(C=C); 130.92, 131.62, 134.86, 136.32, 137.51 (C of thiophene,
C(15)); 149.15, 149.21 (C(13a), C(17a)).
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Received May 16, 2008;
in revised form February 19, 2009