Reactions of Dichloroethenes with Sulfur in the System Hydrazine Hydrate–KОН

Article abstract of DOI:10.1134/S1070363218030015

Vinylidene chloride and 1,2-dichloroethene react with sulfur in the system hydrazine hydrate–KОН with the formation of polyvinylenesulfide oligomer of molecular mass 1750–6120 Da containing also vinylenehydrazine and vinylenechloride links in the Z-configuration, and 1,4-dithiine in the yield up to 46%. In aqueous-hydrazine layer polysulfide anions S_n^2– (n = 1–4), mainly S₂^2– were found. The mechanism of formation of oligomers and 1,4-dithiine is suggested, which includes in the first stage dehydrochlorination of dichloroethenes and generation of chloroacetylene.

Full text of DOI:10.1134/S1070363218030015

ISSN 1070-3632, Russian Journal of General Chemistry, 2018, Vol. 88, No. 3, pp. 383–388. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © Е.P. Levanova, V.S. Nikonova, V.А. Grabel’nykh, N.V. Russavskaya, А.I. Albanov, I.B. Rozentsveig, N.А. Korchevin, 2018,
published in Zhurnal Obshchei Khimii, 2018, Vol. 88, No. 3, pp. 353–359.
Reactions of Dichloroethenes with Sulfur in the System
Hydrazine Hydrate–KОН
Е. P. Levanova, V. S. Nikonova, V. А. Grabel’nykh*, N. V. Russavskaya,
А. I. Albanov, I. B. Rozentsveig, and N. А. Korchevin
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
*
e-mail: venk@irioch.irk.ru
Received October 5, 2017
Abstract—Vinylidene chloride and 1,2-dichloroethene react with sulfur in the system hydrazine hydrate–KОН
with the formation of polyvinylenesulfide oligomer of molecular mass 1750–6120 Da containing also
vinylenehydrazine and vinylenechloride links in the Z-configuration, and 1,4-dithiine in the yield up to 46%. In
2
–
2–
2
aqueous-hydrazine layer polysulfide anions S
n
(n = 1–4), mainly S
were found. The mechanism of formation
of oligomers and 1,4-dithiine is suggested, which includes in the first stage dehydrochlorination of
dichloroethenes and generation of chloroacetylene.
Keywords: 1,1(1,2)-dichloroethens, sulfur, unsaturated sulfur-containing oligomers, 1,4-dithiine, hydrazine
hydrate
DOI: 10.1134/S1070363218030015
1
,1-Dichloroethene (vinylidene chloride) 1а and 1,2-
(yield of 1,4-dithiine 17.6%) [5]. The reaction of
dichloroethene 1b are commercially available mono-
mers and reagents [1, 2] promising for the design of
miscellaneous unsaturated structures. Preparation of
unsaturated sulfides on their basis opens wide
possibilities for the synthesis of polyfunctional ligands
for complex formation with transition metal ions, and
elaboration on their basis of new catalysts for homo-
geneous catalysis, promising extractants, and analytical
reagents [3]. However, there are no published data on
direct reactions of dichloroethenes 1а, 1b with
elemental sulfur. Only photochemical reactions of
sulfur with 1,2-dichloroethene 1b leading to dichloro-
thiirane are known [4]. More effectively with com-
Na S·9H O with vinylidene chloride 1а in the same
2
2
system at 80°С afforded a mixture of thiacrown ethers
in total yield of 40% (yield of 1,4-dithiine 13%) [6]. In
[5, 6] the formation of solid insoluble product was also
noted, whose structure was not investigated. In spite of
relatively low yield of 1,4-dithiine and total yield of
cyclic products, these data demonstrate principal
2
–
possibility of participation of S nucleophile in
reactions with dichloroethenes 1а, 1b.
In the present work we have studied the possibility
of synthesis of organosulfur compounds from
dichlorides 1а, 1b by the reaction with sulfur in a basic
reductive system hydrazine hydrate–KОН. In this
system, with the molar ratio KOH : S > 2 a selective
formation of sulfide anions is observed [7] (Scheme 1).
2–
pounds 1а, 1b react sulfide anions S . Thus, by the
reaction of Na S·9H O with Z-1,2-dichloroethene (Z-
2
2
1
b) in acetonitrile during 46 h a mixture of cyclic
products (unsaturated thiacrown ethers) was obtained,
containing from 6 to 27 atoms in the ring (and,
respectively, from 2 to 9 sulfur atoms) in the total yield
of 18%, the smallest-size cycle, 1,4-dithiine, being
formed in 8.6% isolated yield [5]. The addition of
The formed solution of K S in hydrazine hydrate
2
was used in subsequent transformations without
isolation in the individual state. Selective reduction of
2
–
sulfur along Scheme 1 and participation of S anions
0
.4 equiv. of phase transfer catalyst, 15-crown-5, to the
Scheme 1.
reaction mixture allowed in the same conditions
increasing the total yield of cyclic products to 40%
1
8 2 4 2 2 2 2
/4S + 4KOH + N H ·H O → 2K S + N + 5H O
3
83

3
84
LEVANOVA et al.
Scheme 2.
_
S2 + 2
Br
S
_2
−
Br
Scheme 3.
Cl
Cl
Cl
S
1
or
a
_
S, N H4 H O KOH
2
2
_
+ Sn2
Oligomer +
Cl
S
4
3
5
1
b
_
n = 1 4.
in subsequent reactions was proved by an independent
experiment, the reaction of the obtained solution with
Oligomer product 3 was obtained as a beige
powder. Its yield (calculated on the taken sulfur) varies
in a wide range and, apparently, depends not only on
the ratio of the reagents but also on the conditions of
the experiment (temperature, rate of addition of
dichloroethene 1, intensity of stirring, etc.). A high
yield of oligomer 3 (68%) was observed for the molar
ratio 1а : S = 6 : 1 and addition of 1а in the course of
1
-bromopropane leading to dipropylsulfide 2 in 85%
yield (Scheme 2). The corresponding dipropyldisulfide
or -trisulfide were not detected in the reaction mixture.
We have found that sulfur, activated along Scheme
2–
1
1
to anion S , readily reacts with dichlorides 1а and
b at room temperature with the formation of several
7
h at 15–20°С. The maximum yield of the oligomer
products. From the reaction mixture oligomer 3
precipitated in 26–75% yield. After its separation 1,4-
dithiine 4 was obtained by extraction of the filtrate
(
75%) was obtained when cooling the reaction mixture
to 10–15°С and the ratio 1а : S = 2.5 : 1 (Table 1).
(
yield 16–31% of compound 1а and 14–46% of com-
The data of elemental analysis show that all
isolated samples of oligomers, apart from carbon,
hydrogen and sulfur, contain nitrogen (1–8%) and
residual chlorine (from the reaction with 1а, 1.2–3.8%,
pound 1b). The remaining aqueous-hydrazine layer
contained polysulfide anions S , S and even traces
of S4 (Scheme 3).
2
2
–
2–
3
2
–
Table 1. Yields of the reaction products (Scheme 4, 23°C, 5 h)
Amount of used reagents, mmol
Exp. no.
Yield, % (calculated on sulfur)
а
S
KOH
449.2
100.0
124.8
224.0
224.0
500.0
280.7
449.2
124.8
1а (1b)
224.6
150.0
78.0
3
4
5
1
2
3
4
5
6
7
8
9
112.3
25.0
31.2
56.0
56.0
125.0
28.0
112.3
31.2
42
68
75
45
26
48
28
33
44
23
30
23
31
22
16
32
14
46
16
b
c
Traces
Traces
168.0
56.0
16
24
250.0
56.1
14
17
(112.3)
(93.6)
26
Traces
a
b
Yields of polysulfides estimated from the amount of the formed dipropyl polysulfides calculated on Pr
2
S
2
.
Temperature of reaction 15–
c
2
0°C, time 1 h. Temperature of reaction 10–15°C, time 8.5 h.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 3 2018

REACTIONS OF DICHLOROETHENES WITH SULFUR
Table 2. Elemental analysis data for oligomers 3
385
Composition of oligomer 3
Molecular mass
Exp.
no.
found, %
S
calculated, %
Cl
а
formula
C
x
y
C
H
Cl
N
H
S
N
1
2
3
4
5
6
7
8
9
41.34 3.75 44.52 1.20 8.71 C170
40.47 3.88 45.80 5.95 2.44 C112
40.68 4.01 50.38 1.30 4.91 C206
H
H
H
196
126
230
S
S
S
67
48
90
N
N
N
30Cl
14Cl
24Cl
2
2
2
41.85 4.05 44.03 1.45 8.61 66 15 4730 4879
41.03 3.87 46.95 5.98 2.16 47 3450 3278
41.24 3.86 48.10 1.18 5.60 89 12 5460 5999
7
40.87 3.93 43.93 3.27 6.74 C76
41.29 3.76 49.13 3.16 1.26 C186
40.27 3.89 46.53 6.01 1.16 C206
39.44 3.56 44.86 1.28 7.52 C190
H
88
S
31
N
12Cl
2
40.85 3.97 44.49 3.17 7.52 30
41.14 3.68 50.78 3.09 1.30 85
6
6
2260 2235
5730 5430
H
H
H
198
232
222
S
S
S
86
89
78
N
12Cl
2
2
2
N
N
26Cl
32Cl
41.26 3.90 47.59 6.07 1.18 88 13 6120 5997
41.30 4.05 45.26 1.28 8.11 77 16 5966 5526
40.98 3.31 49.49 1.90 4.51 C50
H
52
S
S
23
25
N
N
2
Cl
2
40.32 3.52 49.52 1.88 4.76 22
40.76 4.06 42.51 3.65 8.91 24
1
6
1753 1489
2030 1886
41.00 3.93 43.93 3.27 6.74 C64
H
76
12Cl
2
a
Corresponds to the exp. no. in Table 1.
–
1
–1
with 1b, 3.2–4.5%). Assuming that the chlorine atoms
are located at the ends of macromolecule of the formed
oligomer as –СН=СНСl fragments, we can calculate
the average molecular mass of the oligomeric product
3440 cm (ν , single wide band) and 1615–1625 cm
NH
(δ ) allows assuming the presence of –NH–NH–
NH
fragments attached to the double bond in the structure
of the oligomer [10] that corresponds to the structure
of the oligomer given above.
(
cf. [8], see Table 2). For the oligomer from vinylidene
chloride 1а it is 2260–6120 Da, and for 1,2-
dichloroethene 1b, 1750–2000 Da. It can be assumed
that the principal motif of the oligomer macro-
molecules forming the polymeric chain is vinylene –
СН=СН– to the ends of which are attached the atoms
of sulfur, nitrogen and chlorine. Based on this, the
structure of the oligomer can be represented as follows:
1
,4-Dithiine 4 formed in the course of the reaction
(
Scheme 3) was the subject of both synthetic and
theoretical studies [11, 12]. The earlier elaborated
methods for its synthesis, as a rule, were based on the
use of difficultly accessible reagents [11]. Thus, it was
synthesized in 47% yield along with a unidentified
product by the reaction of Z-1,2-dichloroethene with
sodium Z-1,2-ethenedithiolate in dry DMSO at 20°С
x y
ClCH=CH–S–(CH=CH–S) –(CH=CHNHNH–) CH=CHCl
[
13]. We have used more available reagents and,
In the literature, the synthesis and properties of
polyvinylene sulfides were described having the E and
Z-configuration of vinylene fragments by the reaction
of polycondensation of sodium E or Z-ethenedithiolate,
respectively, with the E and Z-1,2-dichloroethene 1b in
DMSO at 40°С [9]. The IR spectra of polyvinylene
sulfides with different configuration of the vinylene
fragment are substantially different; in particular, in
the spectrum of the Е-isomer an intense band at
besides, product 4 is easily isolated by extraction of the
aqueous-hydrazine layer by diethyl ether after separation
of oligomer 3.
The formation of polysulfide anions 5 in the
aqueous-hydrazine solution remaining after separation
of products 3 and 4 was proved by their reactions of
alkylation with 1-bromopropane with identification of
the products of alkylation (Scheme 4).
–
1
9
10 cm is present δ(=СН), which is lacking for the
Using the methods of NMR spectroscopy and chro-
matomass spectrometry, we identified dipropylpoly-
polymer with the Z-configuration [9]. In the IR spectra
of all samples of oligomer 3 the absorption in this
region is absent, which is indicative of the Z-
configuration of the vinylene links in the chain. The
presence in the IR spectra of oligomers 3 the bands at
Scheme 4.
2
−
Br
Sn
S + 2
n
_2
−
Br
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 3 2018

3
86
LEVANOVA et al.
Scheme 5.
S2−
_Cl−
7
_
S
OH−
1
а, 1b
Cl
_
−
_
Cl , H O
2
−
6
H
2
NNH
2
, OH
6
NH NH2
NH NH
_
−
_
_HCl
Cl , H O
2
8
9
sulfides with n = 1–4. The major product of alkylation
was dipropyldisulfide. From Н NMR data, the
vinylenehydrazine fragments–CH=CH–NH–NH– in
the formed oligomer chain. Sun and Yang [6]
suggested the mechanism of formation of unsaturated
thia-crown ethers from vinylidene chloride and sodium
sulfide, whose key step was substitution of chlorine
1
average ratio of products Pr S : Pr S : Pr S : Pr S
2
2
2
2
3
2 4
was 1 : 3 : 0.5 : traces.
The formation of similar products (3–5) when using
vinylidene chloride 1а and the two isomers of 1,2-
dichloroethene 1b is indicative of the same mechanism
of their transformations in the system S/N H ·H O–
–
atoms by NaS anions with the formation of sodium
1
1
,1-ethenedithiolate, which further isomerizes to the
,2-isomer. However, this mechanism seems doubtful
2
4
2
because it is based on nontrivial and not evident
assumptions about the ease of nucleophilic substitution
of chlorine atoms at the double bond and about the
KOH. We believe that the first step of these
transformations is dehydrochlorination of compounds
1
а, 1b under the action of alkali resulting in the
–
ready stereoselective migration of the NaS group in
formation of chloroacetylene 6 (Scheme 5). Base-
induced elimination of НСl from dichloroderivatives
of the type 1а, 1b with the formation of chloro-
acetylenes is well known [2, 14]. An indirect confirma-
tion of this in our case was, first, emergence of flashes
at the outlet of condenser (cf. [2]) when performing the
reaction of vinylidene chloride 1а with the system
N H ·H O/KOH without introduction of sulfur (blank
ethenedithiolates.
The most probable route of the formation of 1,4-
dithiine 4 includes preliminary formation of diethynyl-
sulfide 10, which suffers cyclization involving sulfide
anions (Scheme 6).
The transformation 10 → 4 by the reaction of com-
pound 10 with sodium sulfide in the mixture of liquid
ammonia and methanol (2 : 1) at –30°С in 68% yield
was described in the literature [18].
2
4
2
experiment). Another indication was the absence of
reaction of compound 1а with sulfur when activating it
by the system hydrazine hydrate–monoethanolamine,
which is also used in the synthesis of organosulfur
compounds [7, 15] but has much lower basicity,
apparently, not sufficient for dehydrochlorination of
dichloroethenes 1а, 1b. Chloroacetylene 6 is a highly
reactive species [14] where the chlorine atoms are
easily replaced by sulfide anions or by excess
hydrazine (Scheme 5).
In the reaction by Scheme 1 sulfur is reduced to
sulfide anions, but in the aqueous-hydrazine layer
remaining after the separation of products 3 and 4
2
2
–
2–
3
2–
4
anions S
, S
, and even S
are present. Their
formation can be due to the oxidation of sulfide anions.
The oxidation process with participation of air oxygen
2
n
–
is low probable, because polysulfides S
are formed
also in an inert atmosphere (in argon), as well as
because of the presence in the reaction mixture of a
strong reducing agent, hydrazine, which is readily
oxidized by oxygen to diimide in alkaline medium
The formation of macromolecules of oligomer 3,
apparently, proceeds with the participation of chloro-
acetylene 6, ethynethiolate anions 7, and substituted
hydrazines 9 by addition of thiolate anions 7 to the
triple bond of intermediates 6 and 9. This reaction
proceeds as the trans-addition with the formation of
Z-adducts [16]. The addition of nitrogen-containing
[19]. It is known [20] that with lowering pH of the
solution the reaction in which hydrazine acts as an
oxidant becomes thermodynamically possible. The
–
nucleophiles and НО anions to the triple bond occurs,
Scheme 6.
as a rule, in the presence of catalysts, IIB group metal
compounds [17] and, therefore, is hardly probable in
our case. The earlier shown formation of macrocyclic
structures [5, 6] can be prevented by the presence of
S
S2 , 2H O
−
2
5
+ 6
4
_Cl−
_2OH−
10
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 3 2018

REACTIONS OF DICHLOROETHENES WITH SULFUR
387
Scheme 7.
+ 2S + 2H O → 2NH
40–50°С, extracted with ether (5×50 mL). The extract
2
–
2–
2
–
was washed with water, dried over MgSO and the
N
2
H
4
2
3
+ S
+ 2OH ,
2–
3
4
1
solvent was removed. Yield 12.5 g (85%). Н NMR
2–
2–
2
–
N
2
H
4
+ S + S
+ 2H
2
O → 2NH
3
+ S
+ 2OH ,
3
spectrum, δ, ppm: 0.97 t (3H, СН , J = 7.4 Hz), 1.59
3
2
2
–
2–
4
–
3
3
N
2
H
4
+ 2S
+ 2H
2
O → 2NH
3
+ S
+ 2OH .
sext (2Н, ССН С, J = 7.4 Hz), 2.47 t (2Н, СН S, J =
2
2
1
3
7
2
1
.4 Hz). С NMR spectrum, δ, ppm: 13.50 (СН3),
3.05 (ССН С), 34.21 (СН S). Mass spectrum, m/z:
possibility of oxidation of some organic and inorganic
sulfur compounds by hydrazine was mentioned in the
literature [21–23]. Possibly, due to lowering рН of the
medium due to dehydrochlorination of dichloroethenes
2
2
+·
18 [M ].
General procedure for the reaction of dichloro-
ethenes 1а, 1b with sulfur in the system hydrazine
hydrate–alkali. To the solution of KOH in hydrazine
hydrate the required amount of powdered sulfur (see
Table 1) was added at stirring. The mixture was stirred
for 2 h at 80–85°С, cooled to 23°С and dichloroethene
1
а and 1b the reactions depicted in Scheme 7 become
viable.
2
–
Anions Sn (n = 2–4) do not enter the reaction with
chloroacetylene 6 or ethyne thiolate 7 and remain in
aqueous–hydrazine solution.
1
а or 1b was added at continued stirring at 23°С for
another 3–6 h (Table 1 shows total time of addition
and stirring). The formed precipitate of oligomer 3 was
filtered off, washed with water, ether and dried. The
yields calculated from the sulfur content in the
product, molecular mass, composition and the data of
elemental analysis for oligomers 3 are shown in Table
Therefore, the occurrence of parallel reactions
shown in Schemes 5–7 does allow attaining high
yields of dithiine 4. Variations of the yield are
determined by the ratio of the rates of oligomer 3
formation and that of 1,4-dithiine 4. In turn, the
occurrence of these reactions depends on a large
number of factors: the nature of dichloroethene, the
temperature of the process, the rate of addition of the
reagents, hydrodynamic conditions, etc. Nevertheless,
the availability of the reagents, mild reaction
conditions, and the ease of isolation of 1,4-dithiine
allow considering the proposed method of its
preparation quite suitable for synthetic purposes.
2
. On heating to 150–175°С, oligomers 3 become dark
–1
and decompose. IR spectrum, ν, cm : 3442, 3024,
1
5
619, 1559, 1384, 1271, 1145, 1013, 805, 771, 640,
1
39. Н NMR spectrum (DMSO-d ), δ, ppm: 6.68 d
6
3
(
=СН–Сl, J = 4.3 Hz), 6.52–6.66 m (=СН–S, =CH–N).
1
,4-Dithiine (4). The reaction mixture after separa-
tion of oligomer 3 was extracted with ether (3×50 mL),
combined extracts were dried over MgSO . After
4
EXPERIMENTAL
removal of the solvent, the residue was practically pure
1
,4-dithiine 4. The yields calculated on sulfur taken for
IR spectra were taken on a Bruker IFS–25 spectro-
the reaction are given in Table 1. The product is a red
1
13
meter in KBr (for oligomers) or in thin layer. Н, С
NMR spectra were registered on a Bruker DPX-400
spectrometer (working frequencies 400.13 and
liquid of bp 78°С (20 c) {68°С (12 mmHg) [18], 77°С
1
13
(17 mmHg) [24]}. Н and С NMR spectra were
given earlier [25].
1
00.62 MHz respectively) in CDCl , chemical shifts
3
Dipropylpolysulfides. Aqueous-hydrazine layer of
green or green-yellow color remaining after separation
of oligomer 3 and extraction of 1,4-dithiine 4 was
treated with excess 1-bromopropane at 40–50°С. After
addition of propylbromide the reaction mixture dis-
colored. By extraction the mixture with ether a mixture
were measured with respect to TMS. Mass spectra
were measured on a Shimadzu GCMS-QP505A chromato-
mass spectrometer (column SPB-5, 60000×0.25 mm),
quadruple mass analyzer, electronic ionization, 70 eV,
temperature of ionic source 190°С, range of detected
masses 34–650 Da.
1
of dipropylpolysulfides was isolated. Н NMR spec-
Dipropylsulfide (2). To a solution containing 26.0 g
0.5 mol) of KOH in 110 mL of hydrazine hydrate,
.0 g (0.125 mol) of powdered sulfur was added in
portions at stirring at 70–85°С. The obtained mixture
was stirred for 2 h at 85–90°С, cooled to 23°С, and
added dropwise to 30.75 g (0.25 mol) of 1-bromo-
propane. The reaction mixture was stirred for 5 h at
trum, δ, ppm: 0.82–1.02 group of triplets (3H, СН
1.50–1.80 group of multiplets (2Н, ССН С), 2.40–2.73
S). С NMR spectrum, δ
ppm: 11.58, 12.94, 13.5, and 13.34 (СН ); 20.14,
22.32, 22.53 and 22.85 (ССН С); 29.35, 33.98, 35.27
and 40.95 (СН S). Mass spectrum, m/z: 118 [Pr S],
150 [Pr ], 182 [Pr
3
),
(
4
2
1
3
group of triplets (2Н, СН
,
С
2
3
2
2
2
+
S
S ], 185 [М – С Н ] .
2 3 2 5
2
2
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 3 2018

3
88
LEVANOVA et al.
ACKNOWLEDGMENTS
This work was performed with the use of
12. Vashchenko, A.V., Kuznetsova, S.Yu., and Somina, L.A.,
J. Struct. Chem., 2012, vol. 53, no. 2, p. 247. doi
0.1134/S0022476612020060
1
equipment of the Baikal Center for Collective Use of
Siberian Branch of Russian Academy of Sciences.
13. Russell, J., Org. Magn. Res., 1972, vol. 4, p. 433.
14. Comprehensive Organic Chemistry, Barton, D.H.R. and
Ollis, W.D., Oxford: Pergamon Press, 1979.
REFERENCES
1
5. Deryagina, E.N., Levanova, E.P., Grabel’nykh, V.A.,
Sukhomazova, E.N., Russavskaya, N.V., and Korche-
vin, N.A., Russ. J. Gen. Chem., 2005, vol. 75, no. 2,
p. 194. doi 10.1007/s11176-005-0197-y
1
. Plate, N.A. and Slivinskii, E.V., Osnovy khimii i tekhno-
logii monomerov (Fundamentals of Chemistry and Tech-
nology of Monomers), Мoscow: Nauka: MAIK “Nauka/
Interperiodika,” 2002.
. Promyshlennye khlororganicheskie produkty. Spravochnik
Industrial Chlororganic Products. Handbook), Oshin, L.A.,
Ed., Moscow: Khimiya, 1978.
. Levanova, E.P., Nikonova, V.S., Rozentsveig, I.B.,
Russavskaya, N.V., Albanov, A.I., and Korchevin, N.A.,
Russ. J. Org. Chem., 2017, vol. 53, no. 8, p. 1186. doi
0.1134/S107042801708005X
. Lown, E.M., Dedio, E.L., Strausz, O.P., and Gunning, N.E.,
J. Am. Chem. Soc., 1967, vol. 89, no. 5, p. 1056. doi
0.1021/ja00981a003
. Tsuchiya, T., Shimizu, T., and Kamigata, N., J. Am.
Chem. Soc., 2001, vol. 123, no. 47, p. 11534. doi
1
1
6. Khimiya atsetilenovykh soedinenii (The Chemistry of
Acetylenic Compounds), Vie, G.G., Ed., Мoscow:
Khimiya, 1973.
2
(
7. Temkin, O.N., Shestakov, G.K., and Treger, Yu.A.,
Atsetilen: Khimiya. Mekhanizmy reaktsii. Tekhnologiya
3
(Acetylene: Chemistry. Mechanisms of Reactions.
Technology), Мoscow: Khimiya, 1991.
1
1
8. Meijer, J., Vermeer, P., Verkruijsse, H.O., and
1
Brandsma, L., Rec. Trav. Chim., 1973, vol. 92, p. 1326.
4
5
9. Deryagina, E.N., Korchevin, N.A., Russavskaya, N.V.,
and Grabel’nykh, V.A., Russ. Chem. Bull., 1998,
vol. 47, no. 9, p. 1827. doi 10.1007/BF02495714
1
2
0. Tur’yan, Ya.I., Okislitel’no-vosstanovitel’nye reaktsii i
potentsialy v analiticheskoi khimii (Oxidation-Reduc-
tion Reactions and Potentials in Analytical Chemistry),
Мoscow: Khimiya, 1989. 248 с.
1
0.1021/ja0102742
. Sun, D.-Q. and Yang, J.-K., Synthesis, 2011, no. 15,
p. 2454. doi 10.1055/s-0030-1260066
. Deryagina, E.N., Russavskaya, N.V., Papernaya, L.K.,
Levanova, E.P., Sukhomazova, E.N., and Korchevin, N.A.,
Russ. Chem. Bull., 2005, vol. 54, no. 11, p. 2473. doi
6
7
2
2
1. Hauptmann, S., Kluge, Ch.-I.M., Selding, K.-D., and
Wilde, H., Angew. Chem., 1965, vol. 77, no. 15, p. 678.
2. Shagun, L.G., Shagun, V.A., Sarapulova, G.I., Er-
molyuk, L.P., and Voronkov, M.G., Russ. J. Org.
Chem., 2003, vol. 39, no. 10, p. 1568.
1
0.1007/S11172-006-0143-0
8
9
. Korchevin, N.A., Russavskaya, N.V., Alekminskaya, O.V.,
and Deryagina, E.N., Russ. J. Gen. Chem., 2002,
vol. 72, no. 2, p. 260. doi 1070-3632/02/7202-0240
2
2
3. Korchevin, N.A., Russavskaya, N.V., Deryagina, E.N.,
and Trofimov, B.A., Doklady Chem., 1998, vol. 363,
no. 2, p. 201.
. Ikeda, Y., Nagoya, I., and Ozaki, M., Synthetic Metals,
4. Parham, W.E., Wynberg, H., and Ramp, F.L., J. Am.
Chem. Soc., 1953, vol. 75, p. 2065. doi 10.1021/
ja01105a013
1
9
987, vol. 21, no. 2, p. 235. doi 10.1016/0379-6779(87)
0092-0
0. Silverstein, R.M., Webser, F.X., and Kiemle, D.J.,
Spectrometric Identification of Organic Compounds,
New York: Wiley, 2005.
1
1
25. Levanova, E.P., Nikonova, V.S., Grabel’nykh, V.A.,
Russavskaya, N.V., Albanov, A.I., Rozentsveig, I.B.,
and Korchevin, N.A., Russ. J. Org. Chem., 2016,
vol. 52, no. 7, p. 1070. doi 10.1134/S1070428016070307
1. Kobayashi, K. and Gajurel, C.L., Sulfur Rep., 1986,
vol. 7, no. 2, p. 123.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 88 No. 3 2018