Bis(1,3-dithiole-2-chalcogenones) and tetrathiafulvalenes in the synthesis of bridged tetrathiafulvalene-containing structures

Article abstract of DOI:10.1134/S1070428007010186

Bis(1,3-dithiole-2-chalcogenones) in which the 1,3-dithiole fragments are linked through various bridging groups were synthesized by different methods. Some of these compounds were converted into substituted tetrathiafulvalenes with bridged 1,3-dithiole rings. The same structures were synthesized from preliminarily prepared symmetric tetrathiafulvalenes containing 2-cyanoethylsulfanyl groups in both 1,3-dithiole rings. Similar spacers were used to bridge two tetrathiafulvalene fragments. Syntheses of the involved initial compounds were described.

Full text of DOI:10.1134/S1070428007010186

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2007, Vol. 43, No. 1, pp. 135–147. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © G.G. Abashev, A.Yu. Bushueva, K.Yu. Lebedev, E.V. Shklyaeva, 2007, published in Zhurnal Organicheskoi Khimii, 2007, Vol. 43,
No. 1, pp. 129–141.
Bis(1,3-Dithiole-2-chalcogenones) and Tetrathiafulvalenes
in the Synthesis of Bridged Tetrathiafulvalene-Containing
Structures
G. G. Abasheva, A. Yu. Bushuevab, K. Yu. Lebedevb, and E. V. Shklyaevac
a Institute of Technical Chemistry, Ural Division, Russian Academy of Sciences, ul. Lenina 13a, Perm, 614990 Russia
e-mail: gabashev@psu.ru
b Perm State University, Perm, Russia
c Institute of Natural Sciences, Perm, Russia
Received December 12, 2005
Abstract—Bis(1,3-dithiole-2-chalcogenones) in which the 1,3-dithiole fragments are linked through various
bridging groups were synthesized by different methods. Some of these compounds were converted into
substituted tetrathiafulvalenes with bridged 1,3-dithiole rings. The same structures were synthesized from
preliminarily prepared symmetric tetrathiafulvalenes containing 2-cyanoethylsulfanyl groups in both 1,3-di-
thiole rings. Similar spacers were used to bridge two tetrathiafulvalene fragments. Syntheses of the involved
initial compounds were described.
DOI: 10.1134/S10704280007010186
Methods of synthesis of tetrathiafulvalene and its
derivatives have been extensively developed over the
past three decades. These compounds are unique
π-electron donors which give rise to electroconductive
organic systems. In fact, radical cation salts and
charge-transfer complexes based on tetrathiafulvalenes
were meant by the term organic metals. Traditionally,
electron-donor properties and crystal structures of sub-
stituted tetrathiafulvalenes themselves were studied.
However, in the recent time, the scope of application
and investigation of tetrathiafulvalene-containing sys-
tems has become much broader; in particular, these
compounds were used as materials for building up
macrocyclic and supramolecular structures [1, 2].
From this viewpoint, an interesting group of tetra-
thiafulvalenes includes structures containing various
bridging moieties (linkers) which differ in both chem-
ical nature and size; such linkers could connect either
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
1
O
O
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
MeS
SMe
RS
SR
RS
SR
2
3
4
R = p-MeC6H4.
135

ABASHEV et al.
136
(CH2)n
( )6
( )6
S
S
S
S
S
S
S
S
S
Me
Me
Me
Me
S
S
S
N
S
N
S
Me
S
S
Me
S
S
5
6
7
n = 5, 6.
O
CH2(CH2)4CH2
O
O
C12H25
O
OC12H25
A
B
C
D
E
S
S
S
S
S
N
N
S
S
S
S
R
S
R
S
S
S
S
S
S
S
R
S
S
S
R
8
9
10
8, R = p-MeC6H4, MeOCO, H; 9, R = MeOCO.
several tetrathiafulvalene molecules (having both
similar and different structures, e.g., structure 1 [2]) or
fragments of a single tetrathiafulvalene molecule to
form cavities (e.g., structures 2 [2], 3, and 4 [3]. In
some cases, bridged are fragments of so-called “ex-
tended” tetrathiafulvalene molecule, i.e., a molecule in
which two 1,3-dithiole fragments of the tetrathiaful-
valene core are linked through an unsaturated spacer
(e.g., structures 5–7) [3].
With the goal of extending the series of available
tetrathiafulvalene structures for subsequent introduc-
tion into conjugated polymers we synthesized a num-
ber of intermediate products with various bridging
groups (fragments A–E). It may appear that fragments
B and C could give rise to strained structures, for the
tetrathiafulvalene and aromatic moieties in the result-
ing compounds are separated by only two atoms
(C and S). Nevertheless, such structures have been
Scheme 1.
(1) CsOH·H2O, 2 equiv
S
R
S
R
S
S
S
(2) X–A–X, 1 equiv
P(OR')3, toluene, xylene
a
A
X
X
b
S
S
R
S
S
CN
X
(1) CsOH·H2O, 2 equiv
DMF
S
S
S
S
NC
CN
(2) X–A–X, 1 equiv
P(OR')3, toluene
a
b
S
S
R
R
A
S
S
S
S
S
S
R
R
X = S, O, Se.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 1 2007

BIS(1,3-DITHIOLE-2-CHALCOGENONES) AND TETRATHIAFULVALENES
137
Scheme 2.
R3
R1
S
S
P(OR')3, toluene
S
S
S
S
S
S
xylene
A
2
+
X
X
X
c
R2
R2
R3
R1
R3
R1
S
S
S
S
S
S
S
S
S
S
A
R2
R2
+
2 symmetric tetrathiafulvalenes
(1) CsOH·H2O, 2 equiv
DMF
R3
S
S
S
S
(2) X–A–X, 1 equiv
CN
2
d
R1
R2
S
X = S, O, Se.
synthesized (compounds 8, 9 [4], and 10 [5]), and their
electrochemical properties have been described. Tetra-
thiafulvalene derivatives including linkers C and D
have not been reported so far.
Two methods are used most frequently for the
synthesis of tetrathiafulvalene structures like 3, 4, and
8–10: trialkyl phosphite-mediated coupling of bis-
(1,3-dithiole-2-chalcogenones) under strong dilution
(path a) [4, 5] and Becher’s method [6] employing
cesium thiolates obtained from β-cyanoethyl deriva-
tives (path b; Scheme 1). To synthesize tetrathiafulva-
lene structures related to compound 1, two paths c and
d may be proposed (Scheme 2).
For this purpose, we have synthesized four groups
of initial compounds: (1) 1,3-dithiole-2-chalcogenones
11–15 containing a β-cyanoethylsulfanyl group;
(2) tetrathiafulvalenes 16 and 17 containing at least
two such groups in different 1,3-dithiole rings of the
tetrathiafulvalene core; (3) tetrathiafulvalenes 18–22
having one or two β-NCCH2CH2S groups in only one
S
S
S
S
S
S
S
S
CN
CN
CN
CN
CN
Se
X
S
X
S
S
S
S
Me
S
SCH2C6F5
SMe
11 [7]
12a, 12b [6, 8]
13 [9]
14a, 14b [10]
S
S
S
S
S
S
S
S
S
CN
NC
CN
X
OMe
MeO
OMe
S
S
S
O
O
O
15a, 15b [8, 11]
16 [11]
S
S
S
S
S
S
S
S
S
S
NC
CN
CN
S
S
S
Me
Me
SCH2COOMe
17 [7]
18
S
S
S
S
S
S
S
S
S
S
S
CN
CN
CN
S
S
SMe
S
S
S
19
20
S
S
S
S
S
S
S
S
S
S
NC
CN
CN
S
MeS
SMe
S
SMe
21 [10]
22 [10]
12, 14, 15, X = S (a), O (b).
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ABASHEV et al.
138
Scheme 3.
S
S
Me
CS2, hexane
5–10°C
MeCHBrCOOH
EtOH
NH
N
S– H2N
N
S
COOH
(1) Ac2O
(2) Et3N
(3) CS2, acetone
S–
S
BrCH2CH2CN
acetone
CN
S
S
S
Br–
N
N
S
Me
Me
23
24
S
S
S
CN
NC
CN
S
S
S
S
Se, NaBH4, EtOH
P(OEt)3
Se
S
S
Me
11
Me
Me
17
1,3-dithiole ring; and (4) bis(halomethyl)arenes as
bridging fragments B–D. Some of these compounds
were reported previously, while compounds 18–22 and
33–36 were synthesized for the first time.
12a, respectively. The reactions were carried out using
triethyl phosphite as reaction medium (Scheme 5). In
each case, a mixture of three products was formed: one
of these was the desired unsymmetrically substituted
tetrathiafulvalene, while the tho others were symmetric
compounds resulting from self-coupling of 1,3-dhitiol-
2-ones 14b and 12b. The mixtures were separated by
either fractional crystallization or column chromatog-
raphy, and the purity of the products was checked by
thin-layer chromatography. Unsymmetrical compound
19 was also synthesized in a different way, via depro-
tection (removal of the NCCH2CH2 group) of com-
pound 20. In both cases, the overall yields of 19 were
approximately similar (about 30%). The main dif-
ficulty in the first method was to isolate and purify
1,3-dithiole-2-tione 14a (precursor of 14b), but separa-
tion of the final product from two concomitant sym-
metric structures was more facile, as compared to the
isolation of tetrathiafulvalene 20 which was the
starting compound in the second procedure.
Tetrathiafulvalene 17 was synthesized in a good
yield (72%) from selone 11 which was prepared from
mesoionic salt 24 [12] (Scheme 3). Tetrathiafulvalene
16 was synthesized according to Scheme 4 [11] start-
ing from 1,3-dithiole-2-thione 15a [8, 11]; the latter
was obtained by methanolysis of 2-thioxodihydro[1,3]-
dithiolo[4,5-b][1,4]dithiin-5(6H)-one (25) which was
prepared in turn by reaction of zinc dithiolate complex
with chloroacetyl chloride [13, 14]. 1,3-Dithiol-2-one
15b was used in the synthesis of unsymmetrical tetra-
thiafulvalene 18; here, the second component was 4,5-
ethylenedisulfanyl-1,3-dithiole-2-thione (-2-one) [15].
Tetrathiafulvalenes 19 and 21 were obtained by
cross-coupling of 1,3-dithiole-2-thione 27 having
a fused bicyclo[2.2.1]heptane fragment {it was pre-
pared by [4 + 2]-cycloaddition of oligo(1,3-dithiole-
2,4,5-trithione) (26) to norbornene [16]} with oxygen
analogs 14b and 12b of 1,3-dithiole-2-thiones 14a and
Bis(chloromethyl)arenes 32a, 32b, 36a, and 36b
that are necessary for the introduction of bridging
Scheme 4.
(1) NaOMe, MeOH
(2) BrCH2CH2CN
S
S
O
S
S
S
S
S
S
S
CN
CN
S
S
O
S
S
COOMe
S
COOMe
25
P(OEt)3
15a
15b
S
S
S
S
S
S
S
S
S
S
S
S
NC
CN
OMe
CN
MeO
OMe
S
S
S
S
O
O
O
16
18
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 1 2007

BIS(1,3-DITHIOLE-2-CHALCOGENONES) AND TETRATHIAFULVALENES
139
Scheme 5.
Hg(OAc)2, AcOH
12a, 14a
12b, 14b
S(CH2)2CN
S
S
S
S
S
S
12b
S(CH2)2CN
S
S
S
S
S
S
S
20
2 symmetric tetrathiafulvalenes
benzene
P(OEt)3
S
S
+
+
S
n
S(CH2)2CN
S
S
S
S
S
26
27
14b
S
SMe
19
2 symmetric tetrathiafulvalenes
(1) CsOH·H2O, 2 equiv, DMF
(2) MeI
20
19
groups B and C were synthesized according to
Scheme 6. By heating a mixture of paraformaldehyde,
morpholine, and benzene-1,2-diol in isopropyl alcohol
we obtained compound 28 [17] which was treated with
methylene bromide in boiling ethanol. 5,8-Bis(mor-
pholinomethyl)-2,3-dihydro-1,4-benzodioxin (29) [18]
thus formed was converted into diester 30 by the
action of acetic anhydride in the presence of sodium
acetate [18]. Hydrolysis of 30 in a mixture of methanol
with tetrahydrofuran and water gave diol 31 [5,8-bis-
(hydroxymethyl)-2,3-dihydro-1,4-benzodioxin]. Treat-
ment of the latter with thionyl chloride in anhydrous
methylene chloride led to the formation of 5,8-bis-
(chloromethyl)-2,3-dihydro-1,4-benzodioxin (32a).
Scheme 6.
O
O
O
O
BrCH2CH2Br
K2CO3, EtOH
OH
OH
O
HO
OH
O
O
i-PrOH
N
N
N
N
+
+
(CH2O)n
N
H
28
29
Ac2O, AcONa
Δ, 60 h
O
O
O
O
O
O
K2CO3, MeOH–THF–H2O (10:5:1)
O
O
HO
OH
Me
Me
30
31
O
O
SOCl2 or CBr4/PPh3, CH2Cl2
X
X
32a, 32b
O
O
RO
N
OR
RO
OR
RO
OR
RO
OR
N
AcO
OAc
HO
OH
X
X
33
34
35
36a, 36b
R = C12H25; X = Cl (a), Br (b).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 1 2007

ABASHEV et al.
140
Scheme 7.
37% aq. (CH2O)n, HCl (gas)
dioxane, 80°C
Cl
Br
Cl
Br
37
(CH2O)n, concd. HBr
AcOH, 90°C
38
Scheme 8.
(1) CsOH·H2O, 2 equiv
(2) HlgCH2YCH2Hlg, 1 equiv
S
S
R
Y
S
R
S
S
S
S
S
CN
2 X
X
X
S
R
11–15
39a–39g
Bis(1,3-dithiole-2-chalcogenones)
Initial compound no.
X
R
Bridge (Y)
CH2CH2CH2CH2 (A)
Product no.
Hlg
Br
Se
Me
11
39a
Se
S
Me
SMe
1,4-Benzodioxin-5,8-diyl (B)
Cl, Br
Cl
11
14a
39b
39c
S
S
S
S
SCH2C6F5
SCH2COOMe
SCH2CH2CN
SMe
9H-Fluorene-2,7-diyl (D)
9H-Fluorene-2,7-diyl (D)
9H-Fluorene-2,7-diyl (D)
CO (E)
Br
Br
Br
Cl
13
39d
39e
39f
39g
15a
12
12
The corresponding bis(bromomethyl) derivative 32b
was obtained from diol 31 by the Appel reaction, i.e.,
by treatment with carbon tetrabromide in the presence
of triphenylphosphine in anhydrous methylene chlo-
ride. Compounds 36a and 36b were synthesized fol-
lowing an analogous scheme.
Using compounds 11–15 we synthesized bis(1,3-di-
thiole-2-chalcogenones) 39a–39g having A–D linkers
(Scheme 8; see table). In the synthesis of selones 39a
and 39b according to a scheme analogous to the pre-
paration of selone 11, i.e., through mesoionic salts
(Scheme 3) and their subsequent reaction with NaHSe
in situ, the final products were heavily contaminated,
and their yields were poor (Scheme 9).
In order to introduce a fluorene bridging moiety we
used either 2,7-bis(chloromethyl)fluorene (37) pre-
pared by chloromethylation of fluorene with 39%
aqueous formaldehyde in dioxane in the presence of
gaseous hydrogen chloride [19] or 2,7-bis(bromo-
methyl)fluorene (38) which was synthesized by
heating fluorene with concentrated hydrobromic acid
and paraformaldehyde in acetic acid (Scheme 7) [20].
Bis(1,3-dithiole-2-thione) 40 having bridging group
E (CH2COCH2) was synthesized in a way similar to
the synthesis of selone 11. Heating of 2 equiv of salt 23
with 1 equiv of 1,3-dichloropropan-2-one in acetone
gave salt 41 which was converted into compound 40
by treatment with aqueous sodium sulfide at 60°C
Scheme 9.
S–
S
A
S
Br(CH2)6Br, 1 equiv
or 32a
S
S
S
S
S
S
[NaHSe]
2
N
N
N
39a, 39b
2Hlg–
Me
Me
Me
23
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 1 2007

BIS(1,3-DITHIOLE-2-CHALCOGENONES) AND TETRATHIAFULVALENES
141
Scheme 10.
O
S–
S
S
ClCH2COCH2Cl
acetone
S
S
S
S
S
S
2
N
N
N
2Cl–
Me
Me
Me
23
41
O
S
S
S
S
S
Na2S, H2O, 50–60°C
S
S
S
Me
Me
40
Scheme 11.
Y
S
Y
S
S
S
S
S
S
S
S
P(OEt)3, toluene, Δ, 3–5 h
S
S
S
S
S
Me
Me
Me
Me
39a, 39b
42a, 42b
O
Y = (CH2)4 (a),
(b).
O
(Scheme 10). However, unlike the preceding steps
which occurred almost quantitatively, the yield at the
final step was very poor (~12%).
taken [4]. The possibility for formation of such tetra-
thiafulvalenes via the above procedure was demon-
strated by the synthesis of tetrathiafulvalenes 8–10, 43,
and 44 [4, 5], which were obtained by coupling of
analogous bis(1,3-dithiol-2-ones) (8, 9) or bis(1,3-di-
thiole-2-thiones) (10, 43, 44).
Some initial bridged bis(1,3-dithiole-2-chalcoge-
nones) were successfully converted into the corre-
sponding bridged tetrathiafulvalenes. Diselones 39a
and 39b were heated with triethyl phosphite in toluene
to obtain tetrathiafulvalenes 42a and 42b, respectively.
This process occurs as if diselone 39 were turned
inside out with formation of the tetrathiafulvalene core
(Scheme 11). The reactions were performed under
strong dilution using a large amount of trialkyl phos-
phite: about 5 ml of P(OEt)3 and 70–80 ml of anhy-
drous toluene per 0.001 mol of bis-chalcogenone were
Tetrathiafulvalene 42a is a red viscous oily sub-
stance; it was also synthesized from compound 17
containing β-SCH2CH2CN groups in different dithiole
rings of the tetrathiafulvalene core (Scheme 12). The
reaction was performed under conditions of very
strong dilution [4]: equal volumes of solutions of inter-
mediate cesium thiolate and 1,6-dibromohexane in
DMF were added simultaneously at a low rate to the
same volume of pure DMF under argon over a long
time. Likewise, by reactions of tetrathiafulvalenes 16
and 21 with 1,6-dibromohexane and 2,7-bis(bromo-
methyl)fluorene, respectively, in strongly dilute solu-
tion we obtained previously unknown bridged tetra-
thiafulvalenes 45 and 46 (Scheme 12).
Me
N
O
S
O
S
S
S
S
S
S
S
S
S
S
S
S
S
S
S
Some dihalogen derivatives (32a and 38) were used
to link fragments of unsymmetric (19, 22) and sym-
metric compounds (21). As a result, we obtained in
a good yield compound 47, which was isolated as
a yellow crystalline substance (Scheme 13). Compound
O
O
N
Me
43
44
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 1 2007

ABASHEV et al.
142
Scheme 12.
(1) CsOH·H2O, 2 equiv, DMF/MeOH
(2) Br(CH2)6Br, 1 equiv
S
S
S
S
S
S
S
S
S
S
S
S
NC
CN
Me
Me
Me
Me
17
42a
(1) CsOH·H2O, 2 equiv
DMF/MeOH
(2) Br(CH2)6Br, 1 equiv
S
S
S
S
S
S
S
S
S
S
S
S
S
NC
MeO
CN
OMe
MeO
O
OMe
S
S
S
O
O
O
16
45
(1) CsOH·H2O, 2 equiv, DMF/MeOH
(2) 2,7-Bis(bromomethyl)fluorene, 1 equiv
S
S
S
S
S
S
S
S
NC
CN
S
S
S
S
MeS
SMe
MeS
SMe
21
46
Scheme 13.
S
S
S
S
S
S
S
(1) CsOH·H2O, DMF
(2) 32a
S
S
S
O
O
S
S
S
S
SMe
CN
SMe
SMe
S
S
S
S
S
S
S
19
47
S
S
S
2
S
S
S
S
S
S
S
O
O
S
27
S
S
S
S
O
O
O
P(OEt)3
Hg(OAc)2, AcOH
SMe
SMe
SMe
SMe
47
O
S
S
39c'
S
S
39c
47 can also be obtained by coupling of chalcogenones
27 and 39c in the presence of triethyl phosphite (for
this purpose, bis-thione 39c was preliminarily con-
verted into oxygen analog 39c'). However, this way
was less effective: the reaction was accompanied by
formation of a large amount of tarry products, presum-
ably via self-coupling of bis(1,3-dithiol-2-one) 39'c.
Moreover, the latter scheme includes two additional
steps, preparation of the oxygen derivative and separa-
tion of the target product from the symmetric coupling
product containing norbornane fragments, though the
latter is soluble very poorly [16].
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BIS(1,3-DITHIOLE-2-CHALCOGENONES) AND TETRATHIAFULVALENES
143
Scheme 14.
(1) CsOH·H2O, MeOH
(2) 38
22
S
S
S
S
S
S
S
S
S
S
S
S
S
S
SMe
MeS
48
(1) CsOH·H2O, MeOH
(2) 38
21
S
S
S
S
S
S
S
S
S
S
S
S
NC
CN
MeS
SMe
MeS
SMe
49
By reaction of 2 mol of tetrathiafulvalene 22 with
1 mol of 2,7-bis(bromomethyl)fluorene (38) we ob-
tained in a good yield bridged bis-tetrathiafulvalene 48
(an orange crystalline substance). The same fluorene
derivative was used to synthesize molecular ensemble
49 in which two molecules of tetrathiafulvalene 21 are
bridged through a 2,7-bis(methylene)fluorene fragment
(Scheme 14).
was filtered off, dried in air, and recrystallized from
acetic acid. Yield 61%, mp 89–90°C. IR spectrum, ν,
1
cm–1: 1060 (C=S), 2240 (C≡N). H NMR spectrum
(CDCl3), δ, ppm: 2.54 s (3H, SCH3), 2.76 t (2H,
CH2CN), 3.09 t (2H, SCH2).
3-(5-Methylsulfanyl-2-oxo-1,3-dithiol-4-ylsul-
fanyl)propanenitrile (14b) [10]. Compound 14a,
1.62 g (0.006 mol), was dissolved in 60 ml of acetic
acid, 1.9 g (0.006 mol) of Hg(OAc)2 was added, and
the mixture was heated until the reaction was complete
[the mixture turned black due to separation of mer-
cury(II) sulfide]. The mixture was filtered while hot
through a fine filter to remove HgS, the filtrate was
cooled and diluted with water, and the precipitate was
filtered off, dried in air, and recrystallized from
ethanol. Yield 57%, mp 60–62°C.
We are now trying to find conditions to obtain
crystals suitable for X-ray crystallographic analysis.
When a solution of tetrathiafulvalene 18 in acetonitrile
was slowly cooled over a period of 10 days, well
shaped yellow needles precipitated.
EXPERIMENTAL
The IR spectra were recorded on a UR-20 spec-
trometer from samples dispersed in mineral oil. The
1H NMR spectra were measured on a Mercury Plus-
300 instrument relative to HMDS as internal reference.
The progress of reactions and the purity of products
were monitored by TLC on Silufol plates (Kavalier).
Silica gel 60 (0.060–0.2 mm, Lancaster) was used for
column chromatography.
2,3-Dihydro-1,4-benzodioxine-5,8-diyldimetha-
nol (31). A suspension of 6.0 g (0.021 mol) of 2,3-di-
hydro-1,4-benzodioxine-5,8-diyldimethyl diacetate
(30) and 7.3 g (0.0525 mol) of K2CO3 in 100 ml of
a MeOH–THF–H2O solvent mixture (10:5:1) was
stirred for 48 h, excess K2CO3 was filtered off and
washed with methanol (50 ml) on a filter, the filtrate
was evaporated, and the residue was recrystallized
from ethanol. Yield 83%, colorless crystals, with
mp 148–150°C. IR spectrum, ν, cm–1: 3270 br (OH).
1H NMR spectrum (CDCl3), δ, ppm: 4.27 s (4H,
OCH2CH2O), 4.47 s (4H, CH2OH), 7.01 s (2H, Harom).
3-(5-Methylsulfanyl-2-thioxo-1,3-dithiol-4-ylsul-
fanyl)propanenitrile (14a) [10]. A solution of 3.04 g
(0.01 mol) of 3,3'-(2-thioxo-1,3-dithiole-4,5-diyldisul-
fanyl)di(propanenitrile) [6, 8] in 30 ml of anhydrous
dimethylformamide was deaerated by purging with
argon over a period of 10 min, and a solution of 1.68 g
(0.01 mol) of cesium monohydrate CsOH·H2O in
10 ml of methanol was added. When the formation of
cesium thiolate was complete (the solution turned dark
red; ~10 min), 0.62 ml (0.01 mol) of methyl iodide
was added, and the mixture was heated for 10–15 min
at 60°C, cooled, and diluted with water. The precipitate
5,8-Bis(chloromethyl)-2,3-dihydro-1,4-benzodi-
oxine (32a). A mixture of 3.4 g (0.017 mol) of com-
pound 31a and 20.2 g (12.2 ml, 0.17 mol) of thionyl
chloride in 300 ml of anhydrous methylene chloride
was heated for 3.5 h. The resulting solution was
washed with water, a solution of sodium hydrogen
carbonate, and water again until neutral reaction, dried
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 1 2007

ABASHEV et al.
144
compound 32a. The solvent was distilled off, and the
over CaCl2, and evaporated. The reaction completion
was checked by IR spectroscopy, following disappear-
ance of the OH absorption band. Yield 59%, colorless
residue was recrystallized from methanol. Yield 43%,
1
colorless crystals, mp 40–41°C. H NMR spectrum
1
(CDCl3), δ, ppm: 0.87 m (6H, CH3), 1.29 m (40H,
CH2), 4.34 t (4H, CH2O), 4.51 s (4H, CH2Cl), 7.14 m
(2H, Harom). Found, %: Cl 12.87. C32H56Cl2O2. Cal-
culated, %: Cl 13.04.
crystals, mp 147–149°C. H NMR spectrum (CDCl3),
δ, ppm: 4.28 s (4H, OCH2CH2O), 4.52 s (4H, CH2Cl),
6.85 s (2H, Harom). Found, %: Cl 30.31. C10H10Cl2O2.
Calculated, %: Cl 30.42.
1,4-Bis(bromomethyl)-2,3-bis(dodecyloxy)ben-
5,8-Bis(bromomethyl)-2,3-dihydro-1,4-benzodi-
oxine (32b). Triphenylphosphine, 0.03 mol, was added
in small portions under vigorous stirring to a suspen-
sion of 0.01 mol of compound 31 and 0.025 mol of
carbon tetrabromide in 150 ml of anhydrous methylene
chloride, cooled to 0°C. The mixture was stirred for 2–
3 h at room temperature, poured into water, and ex-
tracted with methylene chloride, and the organic phase
was separated, washed with water, and dried over
MgSO4. The solvent was removed, and the crystalline
residue was extracted with boiling methanol. The
extract was cooled, and the precipitate was filtered off.
zene (36b) was synthesized as described for compound
1
32b. Yield 47%, mp 61–62°C. H NMR spectrum
(CDCl3), δ, ppm: 0.84 q (6H, CH3), 1.27 m (40H,
CH2), 4.15 t (4H, CH2O), 4.57 s (4H, CH2Br), 7.2 d
(2H, Harom). Found, %: Br 25.17. C32H56Br2O2. Cal-
culated, %: Br 25.26.
1-[4-(2-Cyanoethylsulfanyl)-5-methyl-1,3-di-
thiol-2-ylidene]piperidinium bromide (24) [6, 7].
A mixture of 2.3 g (0.01 mol) of salt 23 and 1.3 g
(0.9 ml, 0.01 mol) of 3-bromopropanenitrile in 100 ml
of acetone was heated for 1 h (until the red color in-
trinsic to the initial salt disappeared). The light yellow
solution was evaporated, and the residue (a red trans-
parent oily substance) was brought into further syn-
thesis without additional purification. Yield ~100%.
1
Yield 44%, mp 183°C. H NMR spectrum (CDCl3), δ,
ppm: 4.33 t (4H, CH2O), 4.43 t (4H, CH2Br), 6.82 s
and 7.20 s (1H each, Harom). Found, %: Br 49.51.
C10H10Br2O2. Calculated, %: Br 49.63.
4,4'-[2,3-Bis(dodecyloxy)benzene-1,4-diyldi-
methyl]dimorpholine (33) was synthesized as de-
scribed in [18] for compound 29. The product was
recrystallized from methanol. Yield 50–60%, colorless
3-(5-Methyl-2-selenoxo-1,3-dithiol-4-ylsulfanyl)-
propanenitrile (11) [7]. A suspension of 0.79 g
(0.01 mol) of amorphous selenium in 50 ml of ethanol
was deaerated by purging with argon over a period of
15 min, excess sodium tetrahydridoborate, 0.76 g, was
added in small portions under stirring until selenium
dissolved almost completely, and an equivalent amount
of an aqueous solution of salt 24 was added in one
portion. A red–brown crystalline product precipitated
and was filtered off, washed with water, and recrys-
tallized from acetic acid. Yield 70%, red lustrous
crystals, mp 98°C.
1
crystals, mp 42–43°C. H NMR spectrum (CDCl3), δ,
ppm: 0.84 t (6H, CH3), 1.29–2.4 m (40H, CH2), 3.45 t
(8H, CH2), 3.62 m (12H, CH2O), 3.93 s (4H, CH2N),
7.05 m (2H, Harom).
2,3-Bis(dodecyloxy)benzene-1,4-diyldimethyl
diacetate (34) was synthesized as described in [18] for
compound 30. Yield 53%, mp 30–31°C. IR spectrum,
1
ν, cm–1: 1740 (C=O). H NMR spectrum (CDCl3), δ,
ppm: 0.9 t (6H, CH3CH2), 1.30 m (40H, CH2), 2.13 s
(6H, CH3CO), 4.06 t (4H, OCH2CH2), 5.18 s (4H,
CH2OCO), 7.05 m (2H, Harom).
Bis(1,3-dithiole-2-selones) 39a and 39b (general
procedure). A solution of 0.003 mol of compound 11 in
65 ml of anhydrous methanol was deaerated by purg-
ing with argon over a period of 10 min, a solution of
0.003 mol of cesium monohydrate in 10 ml of metha-
nol was added dropwise, and the mixture was heated
until it became homogeneous (for about 10 min). The
resulting cesium thiolate solution was cooled to room
temperature, 1.5 mmol of 1,6-dibromohexane (39a) or
5,8-bis(chloromethyl)-2,3-dihydro-1,4-benzodioxine
(39b) was added, and the precipitate was filtered off
and dried in air.
2,3-Bis(dodecyloxy)benzene-1,4-diyldimethanol
(35) was synthesized as described above for compound
31. After removal of the solvent, the residue was
purified by recrystallization from ethanol. Yield 84%,
colorless crystals, mp 65–66°C. IR spectrum, ν, cm–1:
3380 br, 3350 sh. 1H NMR spectrum (CDCl3), δ, ppm:
0.83 t (6H, CH3), 1.23 m (40H, CH2), 2.25 s (2H, OH),
4.05 t (4H, CH2CH2O), 4.71 s (4H, CH2OH), 7.18 m
(2H, Harom). Found, %: C 75.72. C32H58O4. Calculated,
%: C 75.84.
4,4'-(Hexamethylenedisulfanyl)bis(5-methyl-1,3-
dithiole-2-selone) (39a). Yield 48%, orange–brown
crystals, mp 111–112°C. H NMR spectrum (CDCl3),
1,4-Bis(chloromethyl)-2,3-bis(dodecyloxy)ben-
zene (36a) was synthesized as described above for
1
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BIS(1,3-DITHIOLE-2-CHALCOGENONES) AND TETRATHIAFULVALENES
145
δ, ppm: 1.2–1.6 m (8H, CH2), 2.30 s (6H, CH3), 2.72 t
(4H, SCH2). Found, %: S 35.99. C14H18S6Se2. Cal-
culated, %: S 35.86.
(CDCl3), δ, ppm: 2.82 t (4H, CH2CN), 3.10 t (4H,
SCH2), 3.32 s and 3.46 s (2H each, SCH2), 3.83 m (2H,
CH2), 7.0–7.7 m (6H, fluorene). Found, %: S 46.13.
C27H20N2S10. Calculated, %: S 46.26.
4,4'-[2,3-Dihydro-1,4-benzodioxine-5,8-diylbis-
(methylenesulfanyl)]bis(5-methyl-1,3-dithiole-2-
selone) (39b). Yield 76%, orange crystals, mp 121–
1,3-Bis(5-methylsulfanyl-2-thioxo-1,3-dithiol-4-
ylsulfanyl)propan-2-one (39g). Yield 95%, mp 139–
140°C (from AcOH). IR spectrum, ν, cm–1: 1705
1
122°C. H NMR spectrum (CDCl3), δ, ppm: 1.99 s
1
(6H, CH3), 3. 83 s (4H, SCH2), 4. 18 s (4H,
OCH2CH2O), 6.58 s (2H, Harom). Found, %: S 31.40.
C18H16S6Se2. Calculated, %: S 31.30.
(C=O), 1060 (C=S), 2230 (C≡N). H NMR spectrum
(DMSO-d6), δ, ppm: 2.92 t (4H, CH2CN), 3.24 t (4H,
SCH2), 4.25 s (4H, SCH2CO). Found, %: S 66.70.
C11H10OS10. Calculated, %: S 66.96.
Bis(1,3-dithiole-2-thiones) 39c–39g (general
procedure). A solution of 0.003 mol of 1,3-dithiole-2-
thione 12–15 in 50–70 ml of anhydrous methanol was
deaerated by purging with argon, a solution of
0.003 mol of CsOH·H2O in 10 ml of methanol was
added dropwise, and the mixture was heated for
10 min until it became homogeneous. The resulting
cesium thiolate solution was cooled to room tempera-
ture, and 0.0015 mol of the corresponding dihalogen
derivative [5,8-bis(chloromethyl)-2,3-dihydro-1,4-ben-
zodioxine, 2,7-bis(bromomethyl)fluorene, or 1,3-di-
chloropropan-2-one] was added. When the reaction
was complete (TLC; the mixture turned yellow–
brown), the solvent was removed, and the residue was
recrystallized from appropriate solvent.
1,3-Bis(5-methyl-2-piperidinio-1,3-dithiol-4-yl-
sulfanyl)propan-2-one dichloride (41). A solution of
0.63 g (0.005 mol) of 1,3-dichloropropan-2-one in
100 ml of acetone was slowly added under stirring to
a suspension of 2.31 g (0.01 mol) of mesoionic salt 23
in 125 ml of acetone. The resulting light yellow solu-
tion was evaporated, and the residue was brought into
further transformations without purification. Yield
1
100%. H NMR spectrum (CDCl3), δ, ppm: 1.6–1.8 m
(4H, γ-CH2, piperidine), 2.05 s (6H, CH3), 3.01–3.4 m
(8H, β-CH2, piperidine), 3.7 s (SCH2CO), 4.5–4.7 m
(8H, CH2N).
1,3-Bis(5-methyl-2-thioxo-1,3-dithiol-4-ylsul-
fanyl)propan-2-one (40). A solution of 2.51 g
(0.03 mol) of Na2S in 70 ml of water was slowly added
to a solution of 2.9 g (0.005 mol) of salt 41 in 150 ml
of water. During the addition, a bright yellow solid
separated. After 15 min, the mixture was placed into
a bath heated to 50–60°C for 20 min and cooled, and
the precipitate was filtered off, dried in air, and purifi-
ed by recrystallization from ethanol. Yield 21%, decom-
position point 54–55°C. 1H NMR spectrum (CDCl3), δ,
ppm: 2.25 s (6H, CH3), 3.7 s (4H, SCH2CO). Found,
%: S 61.76. C11H10OS8. Calculated, %: S 61.85.
4,4'-[2,3-Dihydro-1,4-benzodioxine-5,8-diylbis-
(methylenesulfanyl)]bis(5-methylsulfanyl-1,3-di-
thiole-2-thione) (39c). Yield 58%, mp 69–70°C.
1H NMR spectrum (CDCl3), δ, ppm: 2.34 s (6H,
SCH3), 3.92 s (4H, SCH2), 4.23 s (4H, OCH2CH2O),
6.64 s (2H, Harom). Found, %: S 54.66. C18H16O2S10.
Calculated, %: S 54.81.
4,4'-[9H-Fluorene-2,7-diylbis(methylenesul-
fanyl)]bis(5-pentafluorophenylmethylsulfanyl-1,3-
1
dithiole-2-thione) (39d). mp 120–125°C. H NMR
spectrum (CDCl3), δ, ppm: 3.78 s (2H, CH2), 3.72–
3.82 m (4H, CH2S), 4.01–4.06 m (4H, SCH2C6F5),
7.17–7.69 m (6H, fluorene). Found, %: S 33.74.
C35H16F10S10. Calculated, %: S 33.85.
4,4'-(1,6-Hexamethylenedisulfanyl)-5,5'-dimeth-
yl-2,2'-bi(1,3-dithiol-2-ylidene) (42a). a. A mixture of
0.33 g (0.6 mmol) of compound 39a and 8 ml of
triethyl phosphite in 70 ml of anhydrous toluene was
heated under argon until the reaction was complete
(initial selone 39a disappeared according to the TLC
data). The solvent was removed under reduced pres-
sure, and the residue was subjected to column chroma-
tography using hexane–methylene chloride (1:1) as
eluent. Yield 48%, red–orange oily substance. 1H NMR
spectrum (CDCl3), δ, ppm: 1.0–1.7 m (8H, CH2),
2.42 s and 2.7 s (3H each, CH3), 4.17 m (4H, SCH2).
Found, %: S 50.65. C14H18S6. Calculated, %: S 50.80.
Dimethyl 5,5'-[9H-fluorene-2,7-diylbis(methyl-
enesulfanyl)]bis[(2-thioxo-1,3-dithiol-4-ylsulfanyl)-
acetate] (39e). mp 147–150°C. IR spectrum, ν, cm–1:
1
1710 (C=O). H NMR spectrum (CDCl3), δ, ppm:
3.73–3.83 m (10H, OCH3, CH2CO), 4.03–4.06 m (4H,
CH2S), 4.05 s (2H, C9H2, fluorene), 7.19–7.66 m (6H,
Harom, fluorene). Found, %: S 43.77. C27H22O4S10. Cal-
culated, %: S 43.85.
5,5'-[9H-Fluorene-2,7-diylbis(methylenesul-
b. A solution of cesium dithiolate prepared from
0.001 mol of compound 17 and 0.002 mol of CsOH·
fanyl)]bis[3-(2-thioxo-1,3-dithiol-4-ylsulfanyl)pro-
panenitrile] (39f). mp 62–65°C. H NMR spectrum
1
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ABASHEV et al.
146
H2O in 40 ml of DMF (argon atmosphere, 1 h at room
temperature) and a solution of 0.001 mol of 1,6-di-
bromohexane in 40 ml of DMF were slowly (over
a period of 2–3 h) and simultaneously added to 70 ml
of preliminarily deaerated DMF under vigorous stir-
ring. The mixture was left overnight at room tempera-
ture, the solvent was removed under reduced pressure,
and the residue was treated as described above in a.
15,25-Dimethyl-5253-dihydro-12H,22H-3,7-dithia-
1(4,2),2(2,4)-di(1,3-dithiola)-5(5,8)-(1,4-benzodi-
oxina)cycloheptaphan-12(22)-ene (42b). A suspension
of 0.66 g (0.001 mol) of compound 39b and 2 ml of
P(OEt)3 in 150 ml of anhydrous xylene was deaerated
by purging with argon over a period of 15 min and was
then heated for 3 h under reflux. The mixture turned
dark orange. The solvent was distilled off under re-
duced pressure, and the brown crystalline residue was
purified by chromatography using methylene chloride
as eluent. Yield 65%, mp 67–69°C. 1H NMR spectrum
(CDCl3), δ, ppm: 1.67 s and 2.02 s (3H each, CH3),
3.77 s (4H, SCH2), 4.21 s (4H, OCH2CH2O), 6.60 br.s
(2H, Harom). Found, %: S 42.18. C18H16O2S6. Calculat-
ed, %: S 42.12.
fulvalene system. When the reaction was complete, the
mixture was cooled to room temperature, the precip-
itate was filtered off and washed with diethyl ether on
a filter, and the product was purified by fractional
crystallization.
3-(5-Methylsulfanyl-2-{3,5,7,9-tetrathiatetra-
cyclo[9.2.1.02, 10.04, 8]tetradec-4(8)-en-6-ylidene}-1,3-
dithiol-4-ylsulfanyl)propanenitrile (19). Yield 43%,
1
orange crystals, mp 148–149°C. H NMR spectrum
(CDCl3), δ, ppm: 1.25 m (4H, CH2CH2, norbornane),
1.65 t (2H, CH2, norbornane), 2.35 s (3H, SCH3),
2.60 m (2H, CH, norbornane), 3.00 t (4H, SCH2-
CH2CN), 3.30 s (2H, SCHCHS). Found, %: S 52.00.
C17H17NS8. Calculated, %: S 52.15.
3,3'-(2-{3,5,7,9-Tetrathiatetracyclo[9.2.1.02,10.04,8]-
tetradec-4(8)-en-6-ylidene}-1,3-dithiol-4,5-diyldisul-
fanyl)bis(propanenitrile) (20). Yield 56%, orange
1
crystals, mp 180–182°C. H NMR spectrum (CDCl3),
δ, ppm: 1.25 m (4H, CH2CH2, norbornane), 1.65 t (2H,
CH2, norbornane), 2.32 t (4H, CH2CN), 2.69 m (2H,
CH, norbornane), 3.05 m (4H, SCH2), 3.33 s (2H,
SCHCHS). Found, %: S 48.22. C19H18N2S8. Cal-
culated, %: S 48.32.
Tetrathiafulvalenes 45 and 46 were synthesized as
described for compound 42a (method b).
3-[2-(4,5-Ethylenedisulfanyl-1,3-dithiol-2-yli-
dene)-5-methylsulfanyl-1,3-dithiol-4-ylsulfanyl]-
propanenitrile (22). Yield 35%, yellow–orange crys-
Dimethyl 5,5'-(1,6-hexamethylenedisulfanyl)-
1
2,2'-bi[(1,3-dithiol-4-ylsulfanyl)acetate] (45). Yield
tals, mp 97–98°C (from MeOH). H NMR spectrum
1
35%, red thick oily substance. H NMR spectrum
(CDCl3), δ, ppm: 2.62 t (2H, CH2CN), 2.95 t (2H,
SCH2), 3.22 s (4H, SCH2CH2S), 3.53 s (2H, SCH2CO),
3.7 s (3H, OCH3). Found, %: S 52.89. C14H13NO2S8.
Calculated, %: S 53.02.
(CDCl3), δ, ppm: 1.38–1.40 m (4H, SCH2CH2CH2),
1.58–1.61 m (4H, SCH2CH2CH2), 2.8 m (4H, SCH2-
CH2CH2), 3.47 s (4H, SCH2CO), 3.69 s (6H, OCH3).
Found, %: S 45.76. C18H22O4S8. Calculated, %: S 45.89.
5,8-Bis{2-(3,5,7,9-tetrathiatetracyclo-
[9.2.1.02,10.04,8]tetradec-4(8)-en-6-ylidene)-5-
methylsulfanyl-1,3-dithiol-4-ylsulfanylmethyl}-2,3-
dihydro-1,4-benzodioxine (47). A flask equipped with
a reflux condenser was charged with 0.08 g (1.6 mmol)
of tetrathiafulvalene 18 in 10 ml of DMF, the mixture
was purged with argon over a period of 10 min, a solu-
tion of 0.03 g (1.6 mmol) of CsOH·H2O in 3–4 ml of
anhydrous methanol was added (the mixture turned
dark red), and the mixture was heated for 30 min at
60°C. The resulting cesium bis-thiolate solution was
cooled to room temperature, and a solution of 0.02 g
(0.8 mmol) of 5,8-bis(chloromethyl)-2,3-dihydro-1,4-
benzodioxine in a minimal amount of anhydrous DMF
was added. After a few minutes, an orange solid
separated and was filtered off and washed with diethyl
15,25-Bis(methylsulfanyl)-12H,22H,59H-3,7-di-
thia-1(4,2),2(2,4)-di(1,3-dithiola)-5(2,7)-fluorena-
cycloheptaphan-12(22)-ene (46). Yield 32%, orange
1
crystalline substance, mp 119–120°C. H NMR spec-
trum (CDCl3), δ, ppm: 2.88 s and 2.92 s (3H each,
SCH3); 3.79 s (2H, 9-H, fluorene); 4.06 m (4H, SCH2);
7.19 m, 7.28 m, 7.43 m, and 7.65 m (6H, fluorene).
Found, %: S 46.49. C23H18S8. Calculated, %: S 46.56.
Unsymmetrical tetrathiafulvalenes 18–20 and 22
(general procedure). A suspension of equimolar
amounts of the corresponding 1,3-dithiole-2-chalco-
genones [4,5-ethylenedisulfanyl-1,3-dithiole-2-thione
and 15a (18) or 14a (22), 27 and 12a (20), or 27 and
14a (19)] in triethyl phosphite [8–10 ml of P(OEt)3 per
0.002 mol of 1,3-dithiole-2-thione] was deaerated by
purging with argon over a period of 10 min and was
then heated for 30 min at 110–130°C. After 5 min, the
mixture turned cherry due to formation of tetrathia-
1
ether. Yield 50%, mp 148–149°C. H NMR spectrum
(CDCl3), δ, ppm: 1.2 t (8H, CH2CH2, norbornane),
1.6 t (4H, CH2, norbornane), 2.2 s (6H, SCH3), 3.3 s
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BIS(1,3-DITHIOLE-2-CHALCOGENONES) AND TETRATHIAFULVALENES
147
Applications, Graja, A., Bułka B.R., and Kajzar, F.,
Eds., NATO Science Series, II, Mathematics, Physics
and Chemistry, 2002, vol. 59, p. 263; Abashev, G.G.,
Shklyaeva, E.V., Tenishev, A.G., Sheremetev, A.B., and
Yudin, I.L., Trudy mezhdunarodnoi konferentsii “Per-
spektivy razvitiya estestvennykh nauk v vysshei shko-
le” (Proc. Int. Conf. “Prospects in the Development of
Natural Sciences at Higher School), Perm, 2001, p. 20.
(4H, SCH2), 3.9 m (4H, CH, norbornane), 4.2 s (4H,
OCH2CH2O), 6.7 s (2H, Harom). Found, %: S 49.25.
C38H36O2S16. Calculated, %: S 49.43.
Compounds 48 and 49 were synthesized in a simi-
lar way from tetrathiafulvalenes 22 and 21 and 2,7-bis-
(dibromomethyl)-9H-fluorene.
2,7-Bis[2-(4,5-ethylenedisulfanyl-1,3-dithiol-2-
ylidene)-5-methylsulfanyl-1,3-dithiol-4-ylsulfanyl-
methyl]-9H-fluorene (48). Yield 42%, mp 115°C.
1H NMR spectrum (CDCl3), δ, ppm: 2.81 s and 2.88 s
(3H each, SCH3), 3.19 s and 3.22 s (4H each,
SCH2CH2S), 3.78 s (2H, 9-H, fluorene), 3.97 s and
4.05 s (2H each, SCH2). Found, %: S 54.70. C33H26S16.
Calculated, %: S 54.83.
8. Abashev, G.G., Russkikh, V.S., and Shklyaeva, E.V.,
Materialy vsesoyuznoi konferentsii “Elektronika organi-
cheskikh materialov” (ELORMA-90) (Proc. All-Union
Conf. “Electronics of Organic Materials), Dombai,
1990, p. 81; Abashev, G.G., Russkikh, V.S., Shklyae-
va, E.V., and Vladykin, V.I., Russ. J. Org. Chem., 1995,
vol. 31, p. 1533.
9. Abashev, G.G., Shklyaeva, E.V., and Lebedev, K.Yu.,
Khimiya i biologicheskaya aktivnost’ sinteticheskikh i
prirodnykh soedinenii. Kislorod- i serosoderzhashchie
geterotsikly (Chemistry and Biological Activity of Syn-
thetic and Natural Compounds. Oxygen- and Sulfur-
Containing Heterocycles), Kartsev, V.G., Ed., Moscow:
IBS, 2003, vol. 1, p. 157.
2,7-Bis{2-[4-(2-cyanoethylsulfanyl)-5-methylsul-
fanyl-1,3-dithiol-2-ylidene]-5-methylsulfanyl-1,3-
dithiol-4-ylsulfanylmethyl}-9H-fluorene (49). Yield
35%, slowly crystallizing dark red oily substance.
1H NMR spectrum (CDCl3), δ, ppm: 2.23–2.49 m
(12H, SCH3), 2.48 t (4H, CH2CN), 2.79 t (4H,
SCH2CH2), 3.63 s (2H, 9-H, fluorene), 3.84–3.90 m
(4H, SCH2), 7.04–7.55 m (6H, fluorene). Found, %:
S 50.26. C37H32N2S16. Calculated %: S 50.41.
10. Simonsen, K.B., Svenstrup, N., Lau, J., Simmonsen, O.,
Mork, P., Kristensen, G.J., and Becher, J., Synthesis,
1996, p. 407.
11. Abashev, G.G., Shklyaeva, E.V., Russkikh, V.S., and
Krol, S., Mendeleev Commun., 1997, p. 155.
This study was performed under financial support
by the Russian Foundation for Basic Research (project
nos. 04-03-96036-Ural, 05-03-32849a).
12. Souzi, A. and Robert, A., Synthesis, 1982, p. 1059.
13. Abashev, G.G., Russkikh, V.S., and Shklyaeva, E.V.,
Khim. Zh. Ural. Univ., 1992, p. 215.
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 1 2007