Zeitschrift für Naturforschung / B / 46 (1991)

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1269
Preparation of Some Bis(alkylthio)bis(alkylseleno)tetrathiafulvalenes
G. C. Papavassiliou*, V. C. Kakoussis, and
D. J. Lagouvardos
Theoretical and Physical Chemistry Institute,
N ational Hellenic Research Foundation, 48,
Vassileos Constantinou Ave., Athens 116/35,
Greece
Z. Naturforsch. 46b, 1269- 1271 (1991);
received November 23, 1990
ethylenedithioethylenediselenotetrathiafulvalene
(lb 2b ) by a four-steps procedure according to
Scheme 2. This is a m odification of the procedure
VIII reported in ref. [8].
RS>^S\
RS.JLS
* Reprint requests to Prof. G. C. Papavassiliou.
Verlag der Zeitschrift für Naturforschung, D-7400 Tübingen
0932 - 0776/91 /0900 -1269/$ 01.00/0
S
SeR
S. ^ SeR
n x=x T SeR
RS S
Ia2a-le2e
RSe.^S.
RSe^S^/ 2
5))' 2
v( "
RS I S
2a2a - 2e2e
la la - le le
/S \/S .
/S ^ ^ S e
/S ^ S
^-Sv^S
/S'^'Se-%
lb2a
la2c
C O -C O O Old2bO O
ld2c
lc2a
C18H37Sn^"S\ / S
ClgH37S S7 XS
/S \^ S e
<SXSXSX J W s X *>
la2b
C18H37S^ S\
Se
C18H37S
S
S
Se'
le2c
le2b
S
In our previous papers the preparations of some
unsymmetrical tetrakis(alkylthio)tetrathiafulvalenes
and similar unsymmetrical 7i-donors have been de­
scribed [1—8]. Also, some similar compounds have
been prepared by others [9-14], Unsymmetrical
tetrakis(alkylthio)tetrathiafulvalenes have been
used for preparation of conducting crystals or con­
ducting Langmuir-Blodgett films (see [8, 11-17]).
In this paper we describe the preparation of
methylenedithioethylenediselenotetrathiafulvalene
(la 2 b ), methylenedithiotrimethylenediselenotetrathiafulvalene (la 2 c), ethylenedithiomethylenediselenotetrathiafulvalene ( l b 2 a), trimethylenedithiomethylenediselenotetrathiafulvalene (lc2 a ),
vinylenedithioethylenediselenotetrathiafulvalene
(Id 2 b), vinylenedithiotrimethylenediselenotetrathiafulvalene (Id 2c), ethylenediselenodioctadecylthiotetrathiafulvalene (le2 b ), trimethylenediselenodioctadecylthiotetrathiafulvalene (le 2 c ), ethylenedithiodioctadecylselenotetrathiafulvalene (lb 2 e)
and trimethylenedithiodioctadecylselenotetrathiafulvalene (lc2 e ) by one-step procedure according
to Scheme 1. Also, we describe the preparation of
SeR
2a-2e
la-le
Tetrathiafulvalenes, 7r-Donors,
Organic Conductors
Methylenedithioethylenediselenotetrathiafulvalene, methylenedithiotrimethylenediselenotetrathiafulvalene, ethylenedithiomethylenediselenotetrathiafulvalene, trimethylenedithiomethylenediselenotetrathiafulvalene, vinylenedithioethylenediselenotetrathiafulvalene, vinylenedithiotrimethylenediselenotetrathiafulvalene,
ethylenediselenodioctadecylthiotetrathiafulvalene, trimethylenediselenodioctadecylthiotetrathiafulvalene, ethylenedithiodioctadecylselenotetrathiafulvalene, trimethylenedithiodioctadecylselenotetrathiafulvalene and ethylenedithioethylenediselenotetrathiafulvalene have been pre­
pared and characterized analytically and spec­
troscopically.
S
Sx / S
S e C ,^ ^ S
^ S ^ S'
S7 XS^SeC18H37 \-S
x /S
SeC18H3]
S7 Xs
SeC]X
18H37
lc2e
lb2e
(a): 2R=CH2 , (b): 2R=CH2 CH2 , (c): 2R=CH2 CH2 CH2
(d): 2R=CH=CH, (e): R=ClgH37
(i): (EtO)3P, -150°C, N2.
Scheme 1.
O X 3
- u c X x X
5
6
1iv
(XXX)
lb2b
i=LDAat -72°C; ii= Seat -72 - 25°C;
iii= ZnCl2, Bu4NBr; iv= BrCH2CH2Br
Schem e 2.
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1270
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Experimental
Preparation o f lb 2 b
Reagents and apparatus
A solution of lithium diisopropylamide (LDA)
was prepared by the dropwise addition of
«-butyllithium in hexane (—1.6 M) (1.7 ml,
2.7 mmol) to a cooled (- 7 2 °C) solution of tetrahydrofuran (30 ml) containing diisopropylamine
(0.35 ml, 2.5 mmol) under argon atmosphere (see
[5] and refs, therein). The addition rate was con­
trolled so that the reaction tem perature did not
rise above -6 5 °C. etln lenedithiotetrathiafulvalene (3) [8, 18] (35.’ mg, 1.2 mmol) was added at
once and the stirring continued for 2 h at -7 2 °C.
To the resulting yellow solution selenium powder
(213 mg, 2.7 mmol) was added at once and then al­
lowed to warm up to ambient tem perature over­
night (18 h). To the resulting red-brown solutionsuspension a solution of Bu4NBr (1.7 g, 5.4 mmol)
and ZnCl2 (0.37 g, 2.7 mmol) in oxygen-free meth­
anol (25 ml) was added with stirring. The stirring
was continued for 2 h and then the solution was
poured into water (500 ml). The resulting precipi­
tate was filtered and washed with water, isopropanol-ether (1:1) (50 ml), boiling benzene, ether
and dried in air. The brown powder, which con­
tained 6 [19] was treated with BrCH2C H 2Br (3 ml)
in aceton (80 ml) and the solvent was evaporated
to dryness. The resulting solid mass was extracted
with CS2 and chrom atographed on silica gel col­
umn (60 cm) to give lb 2 b as a yellow crystalline
solid. Preparative, analytical and UV spectral data
are listed in Table I.
Reagents and apparatus described in our pre­
vious papers [1-8] as well as reagents reported in
[11, 12, 18] were used.
Preparation o f la 2 b , la 2c, l b 2 a, lc 2 a , Id2b,
ld 2 c , le 2 b , le 2 c , lb 2 e and lc 2 e
A solution of 4,5-methylenedithio-l,3-dithiole2-one (la ) (102 mg, 0.5 mmol) and 4,5-ethylenediseleno-l,3-dithiole-2-one (2b) (151 mg, 0.5 mmol)
in triethylphosphite (5 ml) was heated at —150 °C
for 3 h with stirring under a nitrogen atmosphere.
The precipitate was filtered, washed with acetone
and dried in air. Then, it was chrom atographed
on a silica gel column (60 cm) using CS2 as
eluent. It was found that the first fraction is
bis(methylenedithio)tetrathiafulvalene ( la la ) , the
second fraction is the required product (la 2 b )
and the third fraction is bis(ethylenediseleno)tetrathiafulvalene (2b2b). A second crop o f the
product (la 2 b ) can obtained from the filtrate after
concentration to a small volume and chrom atog­
raphy separation. Com pounds la 2 c , lb 2 a , lc 2 a ,
ld 2 b , ld 2 c , le 2 b , le 2 c , lb 2 e , lc 2 e and lc 2 e pre­
pared by the same method. Preparative, analytical
and UV spectral data are listed in Table I.
Table I. Preparative, analytical3 and U V spectral6 data.
Cpd.
Yield m.p.
[%]
[°C]
la 2 b
10.8
285
la 2 c
14.2
212
lb2a
4.3
230
lc2 a
8.4
230
ld2b
12.7
284
ld 2c
8.2
231
le2b
20.4
84
le 2 c
16.5
80
lb 2e
13.6
84
lc 2 e
16.5
86
1b 2 b
11.5
294
C
H
S
[nm]
23.12
(23.27)
25.18
(25.10)
23.28
(23.27)
25.20
(25.10)
25.11
(25.21)
26.82
(26.94)
55.11
(55.23)
55.47
(55.67)
55.31
(55.23)
55.83
(55.67)
24.93
(25.10)
1.03
(1.30)
1.60
(1-67)
1.22
(1.30)
1.53
(1.67)
1.09
(1.26)
1.53
(1.63)
8.29
(8.16)
8.33
(8.25)
8.19
(8.16)
8.18
(8.25)
1.64
(1.67)
41.18
(41.42)
40.12
(40.17)
41.16
(41.42)
40.30
(40.17)
40.26
(40.34)
39.12
(39.18)
20.18
(20.08)
19.73
(19.79)
20.00
(20.08)
19.76
(19.79)
39.97
(40.17)
322
315
320
316
338
338
334
334
314
333
320
a Analysis (%), calculated values are given in
parentheses; h position o f the strongest band in the UV
visible spectral region.
Results and Discussion
Coupling of la ~ 2 e with 2 a - 2 e via triethyl
phosphite (Scheme 1) afforded mixtures of a num ­
ber of the cross-coupling products I a 2 a ~ le 2 e (all
binary combinations) with the corresponding self­
coupling byproducts l a l a - l e l e and 2 a 2 a - 2 e 2 e .
However, only ten of them (la 2 b , la 2 c , lb 2 a ,
lc 2 a , ld 2 b , ld 2 c , le 2 b , le 2 b , le 2 c , lb 2 e and
lc 2 e) were actually prepared and easily separated
from the corresponding self-coupling byproducts;
because, in these cases, there is a considerable dif­
ference in the /^-values (with CS2 on silica gel) of
the corresponding self-coupling byproducts [20],
The com pounds l a 2 a, l b 2 a etc. could be pre­
pared by one at least of the three-steps procedures
reported in [1,4, 6-8]. However, lb 2 b was prepared
by a four-steps procedure (Scheme 2), in a yield close
to that reported in ref. [1]. This procedure could be
applied for preparation unsymmetrical tetraheterafulvalenes, if the /^-values of the corresponding
symmetrical compounds are almost the same.
N otizen
1271
Also, it could be applied for preparation of d4,h4B ED TTTF [21]. The calculated values of half­
wave oxidation potentials [20] of the new com­
pounds were found to be close to those of
bis(ethylenedithio)tetrathiafulvalene (lb lb ) . This
means that the new compounds are good 7z>donors
for preparation of conducting crystals and/or con­
ducting Langmuir-Blodgett films. At present, we
found th at electrocrystallization of la 2 b or chemi­
cal reaction o f solutions o f la 2 b and Bu4N I3 give
black non conducting crystals, while reaction of
solid la 2 b with a solution o f Bu4N I3 in C H 2C12 in
a stopped flask give brown-black conducting crys­
tals after some days. Also, electrocrystallization of
lb 2 a in presence of Bu4N I3 give golden conduct­
ing crystals. However, details on the physical
properties o f these new rc-donors and of their con­
ducting products will be reported elsewhere.
[1] G. C. Papavassiliou, in M. Hanack, S. Roth, and H.
Schier (eds): Proc. Int. Conf. Sei. Techn. Synth.
M etals, Tübingen, 2 .- 7 . Sept., 1990, Synth. Metals,
42, 2535 (1991), and refs, cited therein.
[2] G. C. Papavassiliou, D. J. Lagouvardos, V. C. Kakoussis, and G. A. M ousdis, Z. Naturforsch. 45b,
1216 (1990) and unpublished work concerning the
preparation o f ethylenedioxodioctadecylthiotetrathiofulvalene (m .p. = 80 °C) and similar com ­
pounds.
[3] G. C. Papavassiliou, V. C. Kakoussis, D. J. Lagou­
vardos, and G. A. M ousdis, Mol. Cryst. Liq. Cryst.
181,171(1990).
[4] G. A. M ousdis, V. C. Kakoussis, and G. C. Papa­
vassiliou, in R. M. Metzger, P. Day, and G. C. Pa­
pavassiliou (eds): Proc. NATO-ASI on Low D. Sys­
tems and Mol. Electronics, Spetses, Greece, Aug.
1989, V. 248 B, p. 181, Plenum Press, N ew York, in
press.
[5] G. C. Papavassiliou, V. C. Kakoussis, J. S. Zambounis, and G. A. M ousdis, Chem. Scripta 29, 123
(1989), and unpublished work concerning the prep­
aration o f 4,5-dioctadecylseleno-l,3-dithiole-2-one
and the corresponding symmetrical-TTF (m .p. =
93 °C, see also P. Wang, T. Enoki, K. Imaeda, N .
Iwasawa, H. Yamochi, H. Urayama, and H. Inokuchi, J. Phys. Chem. 93, 5947 (1989)).
[6] G. C. Papavassiliou, V. C. Kakoussis, G. A. M ous­
dis, J. S. Zambounis, and C. W. Mayer, Chem.
Scripta 29, 71 (1988).
[7] G. C. Papavassiliou, G. A. Mousdis, S. Y. Yiannopoulos, and J. S. Zambounis, Chem. Scripta 28, 365
(1988).
[8] G. C. Papavassiliou, G. A. Mousdis, S. Y. Yiannopoulos, V. C. Kakoussis, and J. S. Zambounis,
Synth. Metals 27, B373 (1988) and refs, cited therein.
[9] A. M. Kini, B. D. Gates, S. F. Tytko, T. J. Allen,
S. B. Kleinjan, H. H. Wang, L. K. M ontgomery,
M. A. Beno, and J. M. Williams, Synth. Metals 27,
B 445 (1988).
[10] H. N akano, K. Miyamaki, T. N ogam i, Y. Shirota,
S. Harada, and N. Kasai, Bull. Chem. Soc. Jpn. 62,
2604 (1989); H. N akano, T. N ogam i, Y. Shirota,
S. Harada, and N. Kasai, ibid. 62, 2382 (1989).
[11] J. Richard, M. Vandevyver, A. Barrand, J. P. M o­
rand, L. Lapouyade, P. Delhaes, J. F. Jacquinot,
and M. Roulliay, J. Chem. Soc. Chem. Commun.
1988, 754; A. Ruandel-Teixier, J. Chim. Phys. 85,
1067(1988).
[12] A. Otsuka, G. Saito, T. Nakamura, M. M atsum oto,
Y. Kawabata, K. Honda, M. G oto, and M. Kurahashi, Synth. Metals 27, B575 (1988).
[13] T. N ogam i, H. N akano, S. Ikegawa, K. M iyawaki,
Y. Shirota, S. Harada, and N . Kassai, in G. Saito
and S. Kayoshim a (eds): Springer Proc. in Physics
Vol. 51: The Physics and Chemistry o f Organic
Superconductors, p. 373, Springer-Verlag Berlin,
Heidelberg (1990).
[14] A. Izuoka, S. M atsumiya, and T. Sugawara, in G.
Saito and S. Kagoshima (eds): Springer Proc. in
Physics Vol. 51: The Physics and Chemistry o f
Organic Superconductors, p. 379, Springer-Verlag
Berlin, Heidelberg (1990).
[15] V. E. K orotkov, R. P. Shibaeva, N. D. Kushch, and
E. B. Y ayobskii, in G. Saito and S. Kagoshima
(eds): Springer Proc. in Physics, Vol. 51. The Phys­
ics and Chemistry o f Organic Superconductors,
p. 306, Springer-Verlag Berlin, Heidelberg (1990).
[16] G. Ren, M. Evain, M .-H . W hangbo, M. A. Beno, V.
Geiser, A. M. Kini, H. H. Wang, and J. M. W il­
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179, 259(1989).
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Lett. 1989, 781.
[19] Com pound 6 was not isolated yet in a pure form.
Sometimes, a by-product similar to 6 can be ob­
tained by chromatography separation on silica gel
with C H C I 3 - C H 3 C O C H 3 (1:1) as eluent. It is a
brown solid; UV-visible 350, 530 nm in aceton, 270,
340, 506 nm in methanol (solvent effect). This is a
precursor o f conducting metal 1,2-diselenolanes:
G. C. Papavassiliou to be published.
[20] G. C. Papavassiliou, unpublished work: It was
found that the /^-values as well as the half-wave oxi­
dation potentials o f an unsymmetrical tetraheterafulvalene is the average o f the values o f the corre­
sponding symmetrical ones (see [1] and refs, therein).
[21] C. W. M ayer, J. S. Zam bounis, B. Hilti, E. Minder,
J. Pfeiffer, and G. Ribs, Synth. Metals, in press; J. S.
Zambounis et al. to be published.