Facile syntheses of 4-(2-cyanoethylthio)-1,3-dithiole-2-thione and new electron donors with two TTF units and compounds with bis(1,3-dithiole-2-thione) groups

Article abstract of DOI:10.1055/s-2002-34837

The synthetic conditions for the preparation of 4-(2-cyanoethylthio)-1,3-dithiole-2-thione (1) from TBA₂?[Zn(dmit)₂] were studied. Compound 1 was used to synthesize new electron donors with two tetrathiafulvalene (TTF) units. Other i

Full text of DOI:10.1055/s-2002-34837

PAPER
2177
Facile Syntheses of 4-(2-Cyanoethylthio)-1,3-dithiole-2-thione and
New Electron Donors with Two TTF Units and Compounds with
Bis(1,3-dithiole-2-thione) Groups
S
ynthesis of 4-(2-
h
Cyanoethylt
u
hio)-1,3-dith
n
iole-2-thioneyang Jia, Deqing Zhang,* Xuefeng Guo, Shuhui Wan, Wei Xu, Daoben Zhu*
Organic Solids Laboratory, Center for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences,
Beijing 100080, P. R. China
E-mail: dqzhang@infoc3.icas.ac.cn
Received 30 April 2002; revised 14 June 2002
tion, interesting compounds that are good precursors for
tetrathiafulvalenophanes8 can be also easily prepared
based on the unusual reaction of TBA2 [Zn(dmit)2].3
Herein we report the syntheses of 1 under different condi-
Abstract: The synthetic conditions for the preparation of 4-(2-cya-
noethylthio)-1,3-dithiole-2-thione (1) from TBA2 [Zn(dmit)2] were
studied. Compound 1 was used to synthesize new electron donors
with two tetrathiafulvalene (TTF) units. Other interesting com-
pounds that are good precursors for tetrathiafulvalenophanes were tions and compounds with bis(1,3-dithiole-2-thione)
groups by the facile approach described by us recently3 as
also easily prepared from TBA2 [Zn(dmit)2].
well as the synthesis of new electron donors with two TTF
units. Oxidation potentials of these new electron donors
are also described.
Key words: electron donors, tetrathiafulvalene, cyclophane, 1,3-
dithiole-2-thione, 1,3-dithiole-2-thione-4,5-dithiolate
It was assumed that 4,5-dimercapto-1,3-dithiole-2-thione
(10)3,9 was the important intermediate compound for the
formation of 1 starting from TBA2 [Zn(dmit)2] and 3-bro-
mopropionitrile as shown in Scheme 1. But, when the re-
action was performed in the presence of four equivalents
(based on TBA2 [Zn(dmit)2]) of acids such as acetic acid
and p-toluenesulfonic acid, compound 1 was not detected
in the reaction mixture. By reducing the amounts of acids,
only 4,5-bis(2-cyanoethylthio)-1,3-dithiole-2-thione (11)
separated out in rather low yield and again compound 1
was not found in the reaction mixture. Thus, it may be in-
ferred that pyridine hydrochloride would be a suitable re-
agent, while it is a mild acid and its conjugate base –
pyridine is a mild base, and is essential for the reaction to
generate 1 (Scheme 1). Besides pyridine hydrochloride,
several commercially available ammonium salts and the
mixture of sodium acetate and acetic acid (in 1:1 molar ra-
tio) were tried for the reaction under the same condition as
in the case of pyridine hydrochloride (see Table 1). For
comparison, the yields of 1 and 11 generated from the re-
action (Scheme 1) in the presence of pyridine hydrochlor-
ide were also included in Table 1. In the cases of
ammonium chloride and the mixture of sodium acetate
and acetic acid, compound 1 was not formed and only
compound 11 was obtained in a low yield. This may be at-
tributed to the low solubilities of ammonium chloride and
sodium acetate in the reaction medium (MeCN). But, it
may be also due to the weak acidic character of ammoni-
um chloride and weak basic character of sodium acetate.
On the contrary, the results indicated that the hydrochlor-
ide salts of triethylamine, aniline and p-diaminobenzene
can be employed for the reaction (Scheme 1) to induce the
formation of 1. It is expected that other organic ammoni-
um salts can be also used for the reaction to generate com-
pound 1.
As the key compound for the preparation of tetrathiaful-
valene (TTF) derivatives, 4,5-bis(alkylthio)-1,3-dithiole-
2-thiones can be conventionally synthesized from the
zinc complex of 1,3-dithiole-2-thione-4,5-dithiolate
{TBA2 [Zn(dmit)2], TBA: tetrabutylammonium} or the
anion of 1,3-dithiole-2-thione-4,5-dithiolate generated in
situ.1 In comparison, its analogue, 4-alkylthio-1,3-dithi-
ole-2-thione is not easily accessible.2 We have just recent-
ly reported that 4-alkylthio-1,3-dithiole-2-thione can be
synthesized easily starting from TBA2 [Zn(dmit)2] and
electrophilic reagents such as 3-bromopropionitrile in the
presence of pyridine hydrochloride.3 Since 2-cyanoethyl
is a good protecting group for thiolates,4 4-(2-cyanoeth-
ylthio)-1,3-dithiole-2-thione (1) is a suitable precursor for
the preparation of new electron donors (Figure 1). For ex-
ample, 1 can be converted easily to 4-(2-cyanoethylthio)-
1,3-dithiole-2-one (2) with Hg(OAc)2, and new electron
donor molecules such as 3 and 4 with 2-cyanoethyl group
can be prepared through the cross-coupling of 2 and 4,5-
ethylenedithio-1,3-dithiole-2-thione and 4,5-bis(meth-
ylthio)-1,3-dithiole-2-thione, respectively, in the presence
of trialkyl phosphite.5 By removal of the 2-cyanoethyl
group from 3 and 4 and subsequently reaction with bis-
electrophilic reagents, new electron donors such as 5–9
(Figure 1) with two TTF units can be obtained from the
easily accessible reactants in a rather straightforward way.
These electron donors are interesting for studies of organ-
ic conductors since higher than one dimensional and dif-
ferent stoichiometric charge-transfer complexes may
result from them.6 In particular, they may be useful for the
construction of molecular spin-ladder systems.7 In addi-
Synthesis 2002, No. 15, Print: 29 10 2002.
Art Id.1437-210X,E;2002,0,15,2177,2182,ftx,en;F03502SS.pdf.
© Georg Thieme Verlag Stuttgart · New York
ISSN 0039-7881

2178
C. Jia et al.
PAPER
Figure 1 The structures of compounds 1–9
Scheme 1 Synthesis of compound 1
As an example, the effect of the quantity of pyridine hy- pionitrile to give 11. Consequently, the yield of 1 will be
drochloride used on the yield of 1 was studied (Table 1). lowered. In short, compound 1 can be synthesized from
When the molar ratio of pyridine hydrochloride versus the easily accessible reactants with four equivalents of an
TBA2 [Zn(dmit)2] was less than four, the yield of 1 was organic ammonium salt in ca. 70% yield.
lower and more 11 was produced. But, if the molar ratio
Based on the above observations and the previous re-
of pyridine hydrochloride versus TBA2 [Zn(dmit)2] was
sults,3,9 the following mechanism was tentatively suggest-
larger than four, the yield of 1 was not increased largely.
ed for the unusual reaction of Zn(dmit)2 ion (Scheme 2).
Compound 10 was supposed to be the key intermediate.
Probably with the help of pyridine, homo-cleavage of
S–H bond generates radical intermediates 10a and 10b.
From 10a, further cleavage of the neighboring S–H bond
and intramolecular migration of hydrogen radical would
lead to the radical intermediate 10c and free sulfur. This is
in accordance with the separation of S8 in the reaction
mixture. Electron-transfer reaction between 10b and 10c
The optimal molar ratio was about four. This may be ex-
plained as following: four equivalents of pyridine hydro-
chloride
probably
converted
most
of
the
TBA2 [Zn(dmit)2] into 10 and liberate the free base (pyri-
dine) which may be involved in the further reaction of 10
to generate 1. If limited amounts of pyridine hydrochlor-
ide were used, probably TBA2 [Zn(dmit)2] was only par-
tially transformed into 10, and the rest of
TBA2 [Zn(dmit)2] will react directly with 3-bromopro-
Synthesis 2002, No. 15, 2177–2182 ISSN 0039-7881 © Thieme Stuttgart · New York

PAPER
Synthesis of 4-(2-Cyanoethylthio)-1,3-dithiole-2-thione
2179
Table 1 Yields of 1 and 11 for the Reaction (Scheme 1) in the Presence of Different Ammonium Salts and the Mixture of Sodium Acetate
and Acetic Acid
Product
CH3CO2Na
NH4Cl
NEt3
AcOH
HCl
HCl
HCl
HCl
HCl
HCl
a
a
1
58%a
45%
35%a
61%
63%a
25%
70%a
17%
35%b
47%
72%c
13%
11
35%
35%
a The reaction was performed with 4 equivalents of ammonium salts and a mixture of NaOAc and AcOH, and the yields were based on the
[Zn(dmit)2].
b The reaction was performed with 1 equivalent of pyridine hydrochloride.
c The reaction was performed with 10 equivalents of pyridine hydrochloride.
should afford 4-thio-1,3-dithiole-2-thione anion (10d), situ, which subsequently reacted with bis-electrophilic re-
which will react with suitable electrophilic reagents to agents such as 1,2-dibromoethane to afford new electron
produce the analogues of 1.
donors with two TTF units 5–9. Analogues of these new
electron donors were synthesized by different multi-step
approaches.10
The oxidation potentials of these new electron donors
were measured with cyclic voltammetry, and the results
are summarized in Table 2. As examples, the cyclic
voltammograms of 7 and 9 are shown in Figure 2. For 5,
6 and 7, three distinct redox-waves were observed. By
comparing with the electrochemical behaviors of analo-
gous electron donors described previously,11 the first two
waves might correspond to two one-electron redox pro-
cesses, and the third was probably due to a two-electron
redox process. On the other hand, only two redox waves
were detected for 8 and 9, which implied that the two TTF
units were independent and they could be oxidized simul-
taneously. Investigations of their charge-transfer salts are
in progress.
Table 2 Redox Potentials of 3–9 Measured by Cyclic Voltammetrya
Compound
E1/21(V)
0.49
0.52
0.37
0.38
0.40
0.44
0.46
E1/22(V)
0.85
E1/23(V)
3
4
5
6
7
8
9
–
0.88
–
0.48
0.80
0.81
0.86
–
0.52
0.54
0.81
Scheme 2 The possible reaction mechanism for the unusual reac-
tion of Zn(dmit)2 ion
0.86
–
Since the 2-cyanoethyl group can be easily removed under
basic condition,4 1 is a potentially good starting com-
pound for the synthesis of new electron donors and related
interesting molecules. For instance, 1 was converted to 2
with Hg(OAc)2, and 3 and 4 can be prepared by the con-
ventional cross-coupling procedure effected by tri(isopro-
pyl) phosphite in yields of 73 and 56%, respectively
(Scheme 3). The deprotection of 2-cyanoethyl group re-
sulted in the formation of the corresponding thiolates in
a All measurements were performed in CH2Cl2 containing 0.1 M
Bu4NPF6, with SCE as the reference electrode, platinum as working
and counter electrodes.
Under similar conditions, TBA2 [Zn(dmit)2] reacted di-
rectly with bis-electrophilic reagents such as 1,3-dibro-
mopropane in the presence of pyridine hydrochloride to
afford compounds 12 and 13 with bis(1,3-dithiole-2-
thione) groups (see Scheme 4). The yields of 12 and 13
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2180
C. Jia et al.
PAPER
Scheme 3 Synthesis of new electron donors 5–9
Figure 2 Cyclic voltammograms of 7 (left) and 9 (right)
were low (about 20%), which was probably due to the for- In summary, on the basis of our recent work, a facile and
mation of compounds with only one 1,3-dithiole-2-thione efficient approach to 1 was developed and the synthetic
group. Although the yields were not high, the present ap- conditions were studied. Its synthetic applications were
proach to compounds with bis(1,3-dithiole-2-thione) demonstrated by the efficient preparations of new electron
groups was rather simple in terms of the easiness to obtain donors 5–9 with two TTF units. Compounds like 12 and
the reactants and perform the reaction and separation in 13 with bis(1,3-dithiole-2-thione) groups can also be syn-
comparison with the synthetic method for their ana- thesized from TBA2 [Zn(dmit)2] in a simple manner.
logues.10a Efforts are underway to optimize the reaction
condition and hence improve the yields. These com-
Melting points were measured with an XT4-100 microscope appa-
ratus and are uncorrected. 1H NMR spectra were recorded on Unity
200 (Varian) and Bruker 300 MHz instruments. IR spectra were re-
corded on a Pekin-Elmer 2000 FT-IR spectrometer. Mass spectra
were recorded on AEI-MS50 for EI-MS, KYKY-ZH-P-5 for FAB-
MS and Beflex III for TOF-MS. Elemental analyses were per-
pounds (e.g. 12 and 13) are good precursors for the
tetrathiafulavenophanes and other interesting molecules
with TTF units.8
Scheme 4 Synthesis of compounds 12 and 13
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PAPER
Synthesis of 4-(2-Cyanoethylthio)-1,3-dithiole-2-thione
2181
formed on a Carlo-Erba-1106 instrument. Cyclic voltammetric
measurements were carried out on an EGDG PAR 370 system.
was subjected to column chromatography with a mixture of petro-
leum ether–CH2Cl2 (2:1, v/v) affording 5 as a yellow crystalline sol-
id. The crude product was recrystallized from CHCl3–hexane to
give yellow micro-needles of 5; yield: 0.089 g (52%); mp 160–
162 °C.
IR (KBr): 2922, 2854, 1636, 1495, 1417, 1261 cm–1.
1H NMR (CDCl3): = 2.44 (s, 12 H, SCH3), 2.96 (s, 4 H,
SCH2CH2S), 6.43 [s, 2 H, CH=CS(S)].
Pyridine hydrochloride and 1,12-dibromodecane were purchased
from Acros Chemicals. 1,11-Dibromo-3,6,9-trioxoundecane was
synthesized from tetraethylene glycol, Ph3P and CBr4 with the con-
ventional method. TBA [Zn(dmit)2] was prepared according to
Ref.1. All other chemicals and solvents were from Beijing Chemical
Company, and were used as received. The petroleum ether used had
a bp range of 60–90 °C.
MS (TOF): m/z = 682 (M+).
4-(2-Cyanoethylthio)-1,3-dithiole-2-thione (1)
This was prepared as described in Ref. 3. Different organic amine
salts as well as NH4Cl and NaOAc/AcOH were tried and the results
are summarized in Table 1.
Anal. Calcd for C18H18S14: C, 31.68; H, 2.66; Found: C, 31.53; H
2.55.
Compounds 6–9 were prepared similar to 5.
6
4-(2-Cyanoethylthio)-1,3-dithiole-2-one (2)
Yield: 41%; yellow micro-needles; mp 113–115 °C.
IR (KBr): 2920, 1645, 1417, 1288 cm–1.
1H NMR (CDCl3): = 2.95(s, 4 H, SCH2CH2S), 3.29 (s, 8 H,
CH2CH2), 6.43 [s, 2 H, CH=CS(S)].
MS (EI): m/z = 678 (M+).
To a solution of compound 13 (0.27 g, 1.23 mmol) in CH2Cl2 (45
mL) was added Hg(OAc)2 (1.18 g, 3.69 mmol) and the mixture was
stirred at 20 °C for 1 h. The white precipitate was removed by fil-
tration through Celite and the filtrate was washed with CH2Cl2. The
solvent was removed to afford compound 2 as a colorless powder;
yield: 200 mg (80%); mp 56–57 °C.
FT-IR (KBr): 2247 (C N), 1632 cm–1 (C=O).
1H NMR (CDCl3): = 2.75 (t, J = 6.8 Hz, 2 H, CH2S), 3.06 (t,
J = 6.8 Hz, 2 H, CH2CN), 7.12 [s, 1 H, CH=CS(S)].
Anal. Calcd for C18H14S14: C, 31.83; H, 2.08. Found: C, 31.80; H,
2.09.
7
MS(EI): m/z = 203 (M+).
Yield: 50%; yellow powder; mp 164–166 °C.
IR (KBr): 3067, 2922, 1632, 1587, 1452, 1407 cm–1.
Anal. Calcd. for C6H5NOS3: C 35.45; H 2.48; N 6.89; Found: C
35.29; H 2.37; N 6.77.
1H NMR (CDCl3): = 3.29 (s, 8 H, CH2CH2), 4.05(s, 4 H, SCH2),
6.22 [s, 2 H, CH=CS(S)], 7.15 (d, J = 5.8 Hz, 2 H, pyridine ring),
7.62 (t, J = 5.8 Hz, 1 H, pyridine ring).
Compound 3
A solution of compound 2 (0.5 g, 2.46 mmol) and 4,5-bis(ethyle-
nethio)-1,3-dithiole-2-thione (1.66 g, 7.39 mmol) in tri(isopropyl)
phosphite (20 mL) was heated to 120 °C under N2 and stirred at this
temperature for 3 h. Column chromatography of the crude reaction
mixture, after the removal of excess tri(isopropyl) phosphite under
reduced pressure, on silica gel with CH2Cl2–petroleum ether (1:1,
v/v) afforded compound 3 as a red powder; yield: 681 mg (73%);
mp 119–120 °C.
FAB-MS: m/z = 756 (M + 1).
Anal. Calcd for C23H17NS14: C, 36.57; H, 2.27; N, 1.86. Found: C,
36.65; H, 2.21; N, 1.73.
8
Yield; 79%; red oil.
IR (KBr): 2920, 2865, 1554, 1469, 1409 cm–1.
1H NMR (CDCl3): = 2.93 (t, J = 4.8 Hz, 4 H, SCH2), 3.28 (s, 8 H,
CH2CH2), 3.63 (‘br’s, 8 H, OCH2CH2O), 3.66 (t, J = 4.8 Hz, 4 H,
OCH2), 6.42 [s, 2 H, CH=CS(S)].
FT-IR (KBr): 2248 cm–1 (C N).
1H NMR (CDCl3): = 2.73 (t, J = 6.9 Hz, 2 H, CH2S), 3.02 (t,
J = 6.9 Hz, 2 H, CH2CN), 3.34 (s, 4 H, CH2CH2), 6.61 [s, 1 H,
CH=CS(S)].
MS(TOF): m/z = 811 (M + 1).
MS (EI): m/z = 379 (M+).
Anal. Calcd for C24H26S14O3: C, 35.53; H, 3.23. Found: C, 35.38; H,
3.20.
Anal. Calcd for C11H9NS7: C, 34.80; H, 2.39; N, 3.69. Found: C,
34.55; H, 2.28; N, 3.32.
9
Compound 4
Yield: 69%; red-brown powder; mp 88–89 °C.
IR (KBr): 2921, 2850, 1555, 1485, 1426 cm–1.
1H NMR (CDCl3): = 1.22–1.38 (m, 16 H, CH2), 1.48–1.72 (m, 4
H, CH2), 2.43 (s, 12 H, SCH3), 2.74 (t, J = 7.6 Hz, 4 H, SCH2), 6.33
[s, 2 H, CH=CS(S)].
This was prepared in a similar way as for 3 and isolated as a red
powder; yield: 56%; mp 102–104 °C.
IR (KBr): 2251 cm–1 (C N).
1H NMR (CDCl3): = 2.42 (s, 6 H, SCH3), 2.58 (t, J = 7.3 Hz, 2 H,
CH2S), 2.93 (t, J = 7.3 Hz, 2 H, CH2CN), 6.61 [s, 1 H, CH=CS(S)].
MS (EI): m/z = 381 (M+).
MS(TOF): m/z = 822 (M+).
Anal. Calcd for C28H38S14: C, 40.84; H, 4.65. Found: C, 41.27; H,
4.71.
Anal. Calcd for C11H11NS7: C, 34.62; H, 2.91; N, 3.67. Found: C,
34.80; H, 2.82; N, 3.58.
Compound 12
Compound 5; Typical Procedure
To a solution of TBA2 [Zn(dmit)2] (940 mg, 1.0 mmol) in MeCN
(50 mL) weree added 1,5-dibromopentane (0.14 mL, 1.0 mmol) and
pyridine hydrochloride (462.2 mg, 4.0 mmol). The mixture was
heated to 50–60 °C and stirred for 2 h at this temperature. The re-
sulting mixture was filtered hot and the remaining solid was further
washed with CH2Cl2 (3 20 mL) for complete extraction of the
To a solution of 4 (0.19 g, 0.5 mmol) in THF (20 mL) under N2 was
added a solution of CsOH H2O (0.994 g, 0.59 mmol) in MeOH (10
mL). The mixture was stirred for 0.5 h at r.t., and then 1,2-dibromo-
ethane (0.02 mL, 0.25 mmol) in THF (5 mL) was added. After stir-
ring for 12 h, the mixture was concentrated in vacuo. The product
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C. Jia et al.
PAPER
(2) (a) Takimiya, K.; Morikami, A.; Otsubo, T. Synlett 1997,
product. The combined filtrate and washings were decolorized by
use of activated charcoal. After removal of the solvent, column
chromatography of the crude reaction mixture on silica gel with
CH2Cl2–petroleum ether (1:4, v/v) as eluent afforded compound 1
as a yellow solid (72 mg, 18%); mp 80–82 °C.
IR (KBr): 1432, 1060, 1046 cm–1.
1H NMR (CDCl3): = 1.60–1.90 (m, 6 H, CH2CH2CH2), 2.85 (t,
319. (b) Wawzonek, S.; Heilmann, S. M. J. Org. Chem.
1974, 39, 511. (c) Falsig, M.; Lund, H. Acta Chem. Scand
1980, 34B, 591.
(3) Jia, C.-Y.; Zhang, D.-Q.; Xu, W.; Zhu, D.-B. Org. Lett.
2001, 3, 1941.
(4) Svenstrup, N.; Rasmussen, K. M.; Hansen, T. K.; Becher, J.
Synthesis 1994, 809.
(5) (a) Bechgaard, K.; Cowan, D. O.; Bloch, A. N. J. Org.
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Etemad, S.; Penney, T.; Patel, V. V. J. Am. Chem. Soc. 1977,
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Liebigs Ann. Chem. 1997, 2177.
J = 7.2 Hz, 4 H, SCH2), 7.02 [s, 2 H, CH=CS(S)].
MS(EI): m/z = 400 (M+).
Anal. Calcd for C11H12S8: C, 33.97; H, 3.02, Found: C, 32.59; H,
2.79.
Compound 13
This was prepared according to the same procedure as above; yield:
21%; yellow powder; mp 72–73 °C.
IR (KBr): 1413, 1331, 1264, 1186, 1061 cm–1.
1H NMR (CDCl3): = 2.01 (quint, J = 7.4 Hz, 2 H, CH2), 2.93 (t,
J = 7.4 Hz, 4 H, SCH2), 7.07 [s, 2 H, CH=CS(S)].
MS(EI): m/z = 372 (M+).
(7) Rovia, C. Chem.–Eur. J. 2000, 6, 1723; and references cited
therein.
(8) (a) Adam, M.; Enkelmann, V.; Räder, H. J.; Röhrich, J.;
Müllen, K. Angew. Chem. Int. Ed. Engl. 1992, 31, 309.
(b) Matsuo, K.; Takimiya, K.; Aso, Y.; Otsubo, T.; Ogura, F.
Chem. Lett. 1995, 523. (c) Yunoki, S.-R.; Takimiya, K.;
Aso, Y.; Otsubo, T. Tetrahedron Lett. 1997, 38, 3017.
(d) Takimiya, K.; Imamura, K.; Shibata, Y.; Aso, Y.; Ogura,
F.; Otsubo, T. J. Org. Chem. 1997, 62, 5567. (e) Lau, J.;
Blanchard, P.; Riou, A.; Jubault, M.; Cava, M. P.; Becher, J.
J. Org. Chem. 1997, 62, 4936.
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(b) Chou, J.-H.; Rauchfuss, T. B.; Szczepura, L. F. J. Am.
Chem. Soc. 1998, 120, 1805.
Anal. Calcd for C9H8S8: C, 29.04; H, 2.17. Found: C, 29.20; H,
2.10.
Acknowledgements
The present research was financially supported by NSFC
(29972044 and 90101025), Chinese Academy of Sciences and State
Key Basic Research Program (G2000077500).
(10) (a) Meziere, C.; Fourmigue, M.; Canadell, E.; Clerac, R.;
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prepared in large scale according to: Steimecke, G.; Sieler,
H.-J.; Kirmse, R.; Hoyer, E. Phosphorus Sulfur 1979, 7, 49.
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Synthesis 2002, No. 15, 2177–2182 ISSN 0039-7881 © Thieme Stuttgart · New York