Chalcogenation of 1,3-Dichlorobut-2-ene with Organic Dichalcogenides in the System Hydrazine Hydrate–Alkali

Article abstract of DOI:10.1134/S1070428018120023

Electron-donor effect of the methyl group in 1,3-dichlorobut-2-ene hampers allylic rearrangement of its primary monochalcogenation products. The use of diphenyl disulfide under harsh conditions (Ph₂S₂–KOH, 1: 10, 75–80°C) makes it possible to obtain a mixture of six bis(phenylsulfanyl)butenes, 1,1-bis(phenylsulfanyl) but-1-ene being the major component. No bis(phenylselanyl) derivatives have been formed on heating up to 80°C. Dipotassium ethane-1,2-dithiolate reacts with 1,3-dichlorobut-2-ene to give a linear product of chlorine substitution at the sp³-carbon atom in two dichlorobutene molecules and a heterocyclic compound, 2-ethylidene-1,4-dithiane (a mixture of E and Z isomers), whose structure is different from the structure of the product obtained from 1,3-dichloropropene under analogous conditions. Mechanisms have been proposed for the formation of the isolated compounds.

Full text of DOI:10.1134/S1070428018120023

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2018, Vol. 54, No. 12, pp. 1754–1759. © Pleiades Publishing, Ltd., 2018.
Original Russian Text © E.P. Levanova, V.S. Nikonova, V.A. Grabel’nykh, N.V. Russavskaya, E.A. Chirkina, A.I. Albanov, I.B. Rozentsveig, N.A. Korchevin,
2018, published in Zhurnal Organicheskoi Khimii, 2018, Vol. 54, No. 12, pp. 1740–1745.
Chalcogenation of 1,3-Dichlorobut-2-ene with Organic
Dichalcogenides in the System Hydrazine Hydrate–Alkali
E. P. Levanovaa,* V. S. Nikonovaa, V. A. Grabel’nykha, N. V. Russavskayaa, E. A. Chirkinaa,
A. I. Albanova, I. B. Rozentsveiga, and N. A. Korchevina
a Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
*e-mail: venk@irioch.irk.ru
Received May 16, 2018; revised May 16, 2018; accepted June 10, 2018
Abstract—Electron-donor effect of the methyl group in 1,3-dichlorobut-2-ene hampers allylic rearrangement
of its primary monochalcogenation products. The use of diphenyl disulfide under harsh conditions (Ph2S2–
KOH, 1:10, 75–80°C) makes it possible to obtain a mixture of six bis(phenylsulfanyl)butenes, 1,1-bis(phenyl-
sulfanyl)but-1-ene being the major component. No bis(phenylselanyl) derivatives have been formed on heating
up to 80°C. Dipotassium ethane-1,2-dithiolate reacts with 1,3-dichlorobut-2-ene to give a linear product of
chlorine substitution at the sp3-carbon atom in two dichlorobutene molecules and a heterocyclic compound,
2-ethylidene-1,4-dithiane (a mixture of E and Z isomers), whose structure is different from the structure of the
product obtained from 1,3-dichloropropene under analogous conditions. Mechanisms have been proposed for
the formation of the isolated compounds.
DOI: 10.1134/S1070428018120023
We previously demonstrated the possibility of
obtaining promising unsaturated organochalcogen
compounds, such as 1-chalcogenyl-3-chloropropenes,
1,3-dichalcogenylpropenes, and 2-ethylidene-1,3-di-
thiolane, from 1,3-dichloropropene, organic dichalco-
genides R2Y2 [1], and poly(ethylene disulfide) [2] in
the system hydrazine hydrate–alkali. The obtained
compounds can be used to synthesize other organo-
chalcogen derivatives [1, 3], as well as highly unsatu-
rated structures containing no chalcogen atoms [4, 5],
e.g., prostaglandin F2α [6]. Taking into account the
high synthetic potential of compounds obtainable from
1,3-dichloropropene, we examined the chalcogenation
of its closest homolog, 1,3-dichlorobut-2-ene (1).
Anderson et al. [7] reported the sulfanylation of com-
pound 1 with benzenethiol in the presence of anhy-
drous potassium carbonate in boiling acetone (12 h;
1–PhSH–K2CO3 ratio 0.9:1.0:1.2. Unlike the corre-
sponding propenyl derivative, the product of substitu-
tion of the allylic chlorine atom by phenylsulfanyl
group (84%) underwent neither thio-Claisen rear-
rangement nor cyclization.
Compound 1 is a commercial product available as
a mixture of Z and E isomers at a ratio of 6.5:1.0
1
(according to the H NMR data). The chalcogenating
agents were generated from organic dichalcogenides,
diphenyl disulfide, diphenyl diselenide, and poly-
(ethylene disulfide), which were preliminarily subject-
ed to reductive cleavage at the S–S or Se–Se bond by
the action of hydrazine hydrate–potassium hydroxide.
Potassium chalcogenolates 2a and 2b or dipotassium
ethane-1,2-dithiolate (2c) were thus formed [8]
Scheme 1.
2Ph2Y2
+
N2H4·H2O
+
4KOH
4PhYK
+
N2
+
5H2O
2a, 2b
Y = S (a), Se (b).
4nKOH
S
SK
2
+
nN2H4·H2O
+
2n
+
nN2
+
5nH2O
S
KS
n
2c
1754

CHALCOGENATION OF 1,3-DICHLOROBUT-2-ENE WITH ORGANIC DICHALCOGENIDES
1755
(Scheme 1) and brought into reaction with dichloro-
butene 1 directly in hydrazine hydrate solution without
isolation.
pound 3a became appreciable only at 75–80°C in the
presence of a large excess of alkali (Ph2S2–KOH ratio
1:10). However, even under these conditions, 10% of
monosubstituted product 3a remains in the reaction
mixture after 5 h. The overall yield of bis(phenyl-
sulfanyl) derivatives was 29%. According to the
GC/MS data, they were represented by six isomers
(m/z 272 [M]+) at a ratio of 10:1:1:0.5:1:1, i.e., one
isomer clearly predominated (yield 19%). By thorough
As reported in [1], 1,3-dichloropropene reacted
with Ph2Y2 under similar conditions to give products
of substitution of either allylic chlorine atom or both
chlorine atoms by phenylchalcogenyl group. It was
convincingly shown [1] that dichalcogenylpropenes
are formed via allylic rearrangement of the initially
formed monosubstitution product; this rearrangement
in the presence of bases involves isomerization of
intermediate carbanions [1, 9]. In the reaction of ben-
zenethiolate with 1,3-dichloropropene, the rearrange-
ment occurs even at 25–35°C [1].
1
analysis of the isomer mixture by H NMR with the
use of two-dimensional NMR techniques, the major
isomer was identified as 1,1-bis(phenylsulfanyl)but-1-
ene (4) (Scheme 2).
Presumably, compound 4 was formed via a series of
transformations (Scheme 2), including deprotonation
of monosubstitution product 3a by the action of alkali
and allylic rearrangement of the resulting carbanion A.
Nucleophilic substitution of the chlorine atom in rear-
rangement product B by phenylsulfanyl group is
hindered due to steric factor and electron-donor effect
of the methyl group which reduces the electrophilicity
of the carbon atom in the CHCl fragment. The same
factors are likely to determine the SN2′ mechanism [9]
of attack of PhS– anion on molecule B with simul-
taneous 1,3-migration of hydrogen, which leads to
the formation of compound 4. Probably, this migration
is favored by the electron-donor effect of the
methyl group.
We have found that the presence of an electron-
donor methyl group in molecule 1 destabilizes the
neighboring carbanionic center [9] and dramatically
affects the reaction of 1,3-dichlorobut-2-ene (1) with
organic dichalcogenides.
Only monosubstitution products 3 were obtained in
the reactions of 1,3-dichlorobut-2-ene (1) with chal-
cogenolates 2a and 2b up to a temperature of 60°C
(Scheme 2). The yield of 3-chloro-1-phenylsulfanyl-
but-2-ene 3a at 25–35°C was 93%, and at 60°C (5 h),
83%. Bis(phenylsulfanyl)butenes appeared in the reac-
tion mixture when the reaction time was prolonged to
10 h at 60°C; in this case, the yield of 3a was 70%.
Benzeneselenolate 2b gave rise to only monosubstitu-
tion product (yield 92%), while the yields of 3b at
25–35°C was 94%.
We failed to unambiguously determine the structure
of the other bis(phenylsulfanyl)butene isomers. Never-
theless, the formation of a large number of isomers
suggests that the presence of a methyl group in the
molecule of bielectrophile 1 essentially changes the
direction of transformations of primary monosubstitu-
tion product 3a in comparison to analogous trans-
formations of 1,3-dichloropropene.
Compounds 3a and 3b were isolated as mixtures of
E and Z isomers at the same ratio as in the initial
dichlorobutene 1. Their structure was confirmed by IR,
NMR (1H, 13C, 77Se), and mass spectra.
The lack of further transformations that could be
expected due to the possibility of allylic rearrangement
suggests that the methyl group in the CH3CCl= frag-
ment hampers migration of the anionic center. The
formation of bis(phenylsulfanyl) derivative from com-
The PhSe substituent reduces the probability of
allylic rearrangement in the propenyl fragment as
compared to phenylsulfanyl group [1]. Therefore,
Scheme 2.
Cl
Cl
Cl
OH–
+
PhYK
–KCl
–H2O
Y = S
Me
Cl
Me
YPh
SPh
Me
SPh
1
2
3a, 3b
A
H
Cl
SPh
SPh
H2O
–OH–
PhS– (SN2')
–Cl–
Me
SPh
Me
SPh
Me
B
4
Y = S (a), Se (b).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 54 No. 12 2018

LEVANOVA et al.
1756
Scheme 3.
Cl
Cl
1
S
Me
S
S–
1
+
Me
S
–Cl–
S
Me
S
Cl
C
5
OH– –H2O
Me
Cl
S–
S
H2O
–OH–
S–
Me
·
S
–Cl–
S
Me
S
D
E
6
monosubstituted product 3b was formed in a high
yield even at 50°C (Scheme 2). Raising the tempera-
ture to 80°C led to the formation of a complex mixture
of compounds, among which we identified selenide 3b
and diphenyl diselenide; the latter is likely to result
from thermal decomposition of bis(phenylselanyl)-
butene derivatives under the given conditions.
compound, 2-ethylidene-1,3-dithiolane [2]. As shown
by quantum chemical calculations, the latter is formed
according to a mechanism similar to the formation of
bis(phenylsulfanyl) derivative 4 (Scheme 2) via allylic
rearrangement and SN2′ reaction [11].
As shown above, the allylic rearrangement of the
monosubstitution product in the reaction of dichloro-
butene 1 even with PhS– anion is fairly difficult to
occur, though, according to the data of [1], the
phenylsulfanyl group is most favorable for allylic
rearrangement among the other examined chalcogenyl
substituents. Therefore, no allylic rearrangement is
The reaction of 1,3-dichlorobut-2-ene (1) with di-
functional dipotassium ethane-1,2-dithiolate gave two
products, linear compound 5 (as a result of substitution
of the allylic chlorine atom in two molecules 1) and
cyclic 2-ethylidene-1,4-dithiane (6) as a mixture of E
and Z isomers (Scheme 3). As expected, linear product
5 contained Z- and E-chlorobutenyl fragments with the
Z/E ratio corresponding to the isomer ratio in initial
compound 1 (~6.5:1).
–
observed in the structure containing an SCH2CH2S
substituent, and no dithiolane derivative is formed
from dichlorobutene 1.
Thus, the formation of compounds 5 and 6 can be
illustrated by Scheme 3. The primary monosubstitution
product C either reacts with the second molecule 1 to
give linear compound 5 or undergoes dehydrochlorina-
tion through intermediate anion D; migration of
hydrogen in the latter and elimination of chloride ion
lead to allene derivative E. Intramolecular nucleophilic
attack of the free thiolate group on the central carbon
atom of the allene fragment of E [10] yields cyclic
product 6. Compounds 5 and 6 were not described
The ratio of compounds 5 and 6 obtained at 25–
35°C strongly depended on the concentration of alkali
in the reaction mixture. When (–SCH2CH2S–)n was
preliminarily treated with a mixture of hydrazine
hydrate and potassium hydroxide at a ratio of (1:10),
compounds 5 and 6 were formed at a ratio of 5:1.
When the ratio N2H4·H2O/KOH was 1:5, the ratio 5/6
changed to 9:1 (yield 59 and 22 wt %, respectively).
Approximately equal amounts of 5 and 6 (5/6 1.1:1.0)
were formed at 50°C (5 h). The Z isomer of 6 pre-
dominated, and the E/Z ratio 1:2 almost did not
depend on the reaction temperature.
1
previously. Their structure was confirmed by IR, H
and 13C NMR, and mass spectra.
The reaction of dichlorobutene 1 with poly-
(methylene disulfide) (7) preliminarily treated with
hydrazine hydrate–potassium hydroxide (7–KOH ratio
1:10, 85–90°C) gave 55% of bis(3-chlorobut-2-en-1-
The lower homolog of 1, 1,3-dichloropropene,
reacted with dipotassium ethane-1,2-dithiolate to give
a linear product and a five-membered heterocyclic
Scheme 4.
Cl
Cl
N2H4·H2O/KOH
21
S
S
CH4
+ K2S
–N2, –H2O
–2KCl
n
Me
S
Me
7
8
n = 10–15.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 54 No. 12 2018

CHALCOGENATION OF 1,3-DICHLOROBUT-2-ENE WITH ORGANIC DICHALCOGENIDES
1757
yl) sulfide (8) containing no SCH2S fragment
(Scheme 4). The formation of sulfide 8 could be
expected since the corresponding sulfide was obtained
in 52% yield in the reaction with more reactive
(than 1) 2,3-dichloroprop-1-ene [12]. In reactions with
unsaturated bielectrophiles, compounds like 8 are
formed as a result of preferential cleavage of poly-
(methylene sulfides) at the C–S bond with generation
of S2– anions in the system hydrazine hydrate–alkali
[13]. The subsequent reaction of K2S with 1,3-di-
chlorobutene 1 yields sulfide 8 (Scheme 4). The latter
was also obtained in 58% yield by adding compound 1
to a solution of sulfur in N2H4·H2O–KOH (S/KOH
ratio 1:2.5) at 25–35°C.
and the residue was subjected to analysis and appro-
priate treatment.
[(3-Chlorobut-2-en-1-yl)sulfanyl]benzene (3a)
was obtained from 4.37 g (0.02 mol) of Ph2S2, 5.61 g
(0.1 mol) KOH, and 2.5 g (0.02 mol) of 1 in 25 mL of
hydrazine hydrate at 25–35°C (5 h). The residue, 3.7 g,
was almost pure compound 3a. Yield 93%, bp 93–
95°C (2 mm); published data [7]: bp 84°C (0.75 mm).
IR spectrum: ν 1659 cm–1 (C=C).
1
Z Isomer. H NMR spectrum, δ, ppm: 2.06 s (3H,
3
CH3), 3.65 d (2H, CH2S, J = 7.2 Hz), 5.57 t (1H,
3
=CH, J = 7.2 Hz), 7.16–7.33 m (5H, Ph). 13C NMR
spectrum, δC, ppm: 26.10 (CH3), 32.04 (CH2), 121.76
(=CCl), 126.19 (=CH), 128.93, 129.57, 131.46, 135.86
(Ph). Mass spectrum, m/z (Irel, %): 200 (16) (37Cl), 198
(40) (35Cl) [M]+.
Thus, unsaturated organochalcogen compounds can
be synthesized from 1,3-dichlorobut-2-ene (1) and
organic dichalcogenides. The presence of a methyl
group in the MeCCl= fragment strongly inhibits
substitution of chlorine at the sp2-hybridized carbon
atom. The reaction of 1,3-dichlorobut-2-ene (1) with
poly(ethylene disulfide) afforded previously unknown
2-ethylidene-1,4-dithiane as a mixture of E and
Z isomers.
1
E Isomer. H NMR spectrum, δ, ppm: 1.84 s (3H,
3
CH3), 3.46 d (2H, CH2S, J = 8.5 Hz), 5.74 t (1H,
3
=CH, J = 8.5 Hz), 7.16–7.33 m (5H, Ph). 13C NMR
spectrum, δC, ppm: 20.61 (CH3), 33.09 (CH2), 123.06
(=CCl), 127.03 (=CH), 129.00, 130.66, 133.22, 135.20
(Ph). Mass spectrum, m/z (Irel, %): 200 (17) (37Cl), 198
(43) (35Cl) [M]+. Found (isomer mixture), %: C 60.52;
H 5.51; Cl 17.61; S 16.04. C10H11ClS. Calculated, %:
C 60.44; H 5.58; Cl 17.84; S 16.13. M 198.71.
EXPERIMENTAL
The IR spectra were recorded on a Bruker IFS-25
[(3-Chlorobut-2-en-1-yl)selanyl]benzene (3b) was
obtained from 2.5 g (0.008 mol) of Ph2Se2, 2.24 g
(0.04 mol) of KOH, and 1.0 g (0.008 mol) of 1 in
10 mL of hydrazine hydrate. The residue, 1.84 g, was
almost pure compound 3b. Yield 94%, bp 95–100°C
(2 mm). IR spectrum: ν 1654 cm–1 (C=C).
1
spectrometer from thin films. The H, 13C, and 77Se
NMR spectra were recorded on a Bruker DPX-400
spectrometer at 400.13, 100.62, and 76.31 MHz,
respectively, using CDCl3 as solvent and tetramethyl-
silane (1H, 13C) or Me2Se (77Se) as internal standard.
The mass spectra were obtained on a Shimadzu
GCMS–QP5050A instrument (SPB-5 column,
60 m×0.25 mm; quadrupole mass analyzer, electron
impact, 70 eV, ion source temperature 190°C, a.m.u.
range 34–650).
1
Z Isomer. H NMR spectrum, δ, ppm: 2.06 s (3H,
3
CH3), 3.64 d (2H, CH2Se, J = 7.9 Hz), 5.67 t (1H,
3
=CH, J = 7.9 Hz), 7.25–7.65 m (5H, Ph). 13C NMR
spectrum, δC, ppm: 25.15 (CH3), 26.17 (CH2), 122.32
(=CCl), 127.21 (=CH), 128.97, 129.74, 133.41, 134.96
(Ph). 77Se NMR spectrum: δSe 337.5 ppm. Mass
spectrum, m/z (Irel, %): 248 (8) (37Cl, 80Se), 246 (18)
(35Cl, 80Se) [M]+.
Reductive cleavage of organic dichalcogenides
and subsequent reaction with 1,3-dichlorobut-2-ene
(1) (general procedure). A required amount of the
corresponding dichalcogenide was added with
vigorous stirring to a solution of potassium hydroxide
in hydrazine hydrate heated to 60°C. The resulting
solution was stirred for 2 h at 80–85°C and cooled to
25°C, and a required amount of 1,3-dichlorobut-2-ene
(1) was added dropwise with stirring. The mixture was
stirred for 5–10 h at a temperature indicated below,
cooled to 25°C, and extracted with diethyl ether
(3×50 mL). The combined extracts were washed with
water and dried over MgSO4, the solvent was removed,
1
E Isomer. H NMR spectrum, δ, ppm: 1.73 s (3H,
3
CH3), 3.46 d (2H, CH2Se, J = 8.7 Hz), 5.83 t (1H,
3
=CH, J = 8.7 Hz), 7.25–7.65 m (5H, Ph). 13C NMR
spectrum, δC, ppm: 25.73 (CH3), 29.75 (CH2), 123.86
(=CCl), 127.84 (=CH), 128.35, 129.36, 132.91, 134.18
77
(Ph). Se NMR spectrum: δSe 349.4 ppm. Mass spec-
trum, m/z (Irel, %): 248 (4.6) (37Cl, 80Se), 246 (9)
(35Cl, 80Se) [M]+. Found (isomer mixture), %: C 48.71;
H 4.53; Cl 14.57; Se 32.19. C10H11ClSe. Calculated,
%: C 48.90; H 4.51; Cl 14.43; Se 32.15. M 245.61.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 54 No. 12 2018

LEVANOVA et al.
1758
of 1 in 70 mL of hydrazine hydrate at 25–35°C. The
1,1-Bis(phenylsulfanyl)but-1-ene (4) was iden-
residue was a yellow liquid, 1.7 g, which was almost
tified in a mixture of isomeric bis(phenylsulfanyl)-
butenes. H NMR spectrum, δ, ppm: 1.05 t (3H, CH3),
2.42 m (2H, CH2), 6.39 t (1H, =CH), 7.20–7.44 m
(10H, Ph). Mass spectrum: m/z 272 (Irel 44%) [M]+.
Calculated: M 272.43.
1
pure compound 8. Yield 55%, bp 89–92°C (2 mm). IR
1
spectrum: ν 1659 cm–1 (C=C). H NMR spectrum, δ,
ppm: E isomer: 2.07 s (3H, CH3), 3.16 d (2H, CH2S,
3J = 8.5 Hz), 5.60 t (1H, =CH, 3J = 8.5 Hz); Z isomer:
3
2.12 s (3H, CH3), 3.27 d (2H, CH2S, J = 7.4 Hz),
1,2-Bis(3-chlorobut-2-en-1-ylsulfanyl)ethane (5)
was obtained from 2.43 g (0.0264 mol) of poly-
(ethylene disulfide), 14.8 g (0.264 mol) of KOH, and
3.29 g of 1 in 65 mL of hydrazine hydrate at 25–35°C.
The residue, 2.73 g, was a mixture of compounds 5
and 6 (59 and 22%, respectively), which were sepa-
rated by vacuum distillation.
5.55 t (1H, =CH, 3J = 7.4 Hz). 13C NMR spectrum, δC,
ppm: Z isomer: 26.18 (CH3), 29.41 (CH2S), 122.33
(CH=), 132.84 (=CCl); E isomer: 20.85 (CH3), 29.67
(CH2S), 123.94 (CH=), 132.84 (=CCl). Mass spec-
trum: m/z 210 (Irel 15%) (35Cl) [M]+. Found, %:
C 45.32; H 5.72; Cl 33.46; S 15.16. C8H12Cl2S. Cal-
culated, %: C 45.51; H 5.73; Cl 33.58; S 15.18.
M 211.15.
Compound 5. bp 150–160°C (2 mm). IR spectrum:
1
ν 1658 cm–1 (C=C). H NMR spectrum, δ, ppm:
b. From 0.8 g (0.025 mol) of sulfur, 3.5 g
(0.0625 mol) of KOH, and 4.68 g (0.0374 mol) of 1
in 15 mL of hydrazine hydrate at 25–35°C. The
residue, 2.28 g, was almost pure compound 8. Yield
58%; the product was identical in boiling point and
spectral parameters to a sample obtained as described
above in a.
4
Z isomer: 2.13 d (3H, CH3, J = 1.2 Hz), 2.71 s (4H,
3
SCH2CH2S), 3.29 d (2H, SCH2C=, J = 7.5 Hz),
3
4
5.54 t.q (1H, =CH, J = 7.5, J = 1.2 Hz); E isomer:
2.08 s (3H, CH3), 2.71 s (4H, SCH2CH2S), 3.17 d (2H,
3
3
SCH2C=, J = 7.9 Hz), 5.62 t (1H, =CH, J = 7.9 Hz).
13C NMR spectrum, δC, ppm: Z isomer: 26.02 (CH3),
29.50 (SCH2C=), 31.10 (SCH2CH2S), 122.41 (=CH),
132.82 (=CCl); E isomer: 20.86 (CH3), 29.79
(SCH2C=), 31.37 (SCH2CH2S), 123.87 (=CH), 132.82
(=CCl). Mass spectrum (two peaks on the chromato-
gram): m/z 270 (35Cl) [M]+. Found, %: C 44.40;
H 5.98; Cl 25.81; S 23.58. C10H16Cl2S2. Calculated, %:
C 44.28; H 5.94; Cl 26.14; S 23.64. M 271.27.
The main results were obtained using the equip-
ment of the Baikal Joint Analytical Center, Siberian
Branch, Russian Academy of Sciences.
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1. Levanova, E.P., Nikonova, V.S., Grabel’nykh, V.A.,
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2-Ethylidene-1,4-dithiane (6). Yield 22%, bp 92–
98°C (2 mm). IR spectrum: ν 1632 cm–1 (C=C).
1
Z Isomer. H NMR spectrum, δ, ppm: 1.77 d.t (3H,
3
5
CH3, J = 6.7, J = 0.8 Hz), 2.99 m (4H, SCH2CH2S),
3.41 d.q (2H, SCH2C=, 4J = 1.1, 5J = 0.8 Hz), 5.69 d.q
3
4
13
(1H, CH=, J = 6.7, J = 1.1 Hz). C NMR spectrum,
δC, ppm: 14.36 (CH3), 29.68, 31.19 (SCH2CH2S),
36.13 (SCH2C=), 125.37 (CH=), 128.26 (=CS). Mass
spectrum: m/z 146 (Irel 100%) [M]+.
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1976, vol. 41, p. 2506.
4. Oshima, K., Yamamoto, H., and Nozaki, H., Bull. Chem.
Soc. Jpn., 1975, vol. 40, p. 1567.
1
5. Carlson, R.G. and Mardis, W.S., J. Org. Chem., 1975,
E Isomer. H NMR spectrum, δ, ppm: 1.68 d (3H,
3
vol. 40, p. 817.
CH3, J = 7.0 Hz), 2.99 m (4H, SCH2CH2S), 3.48 br.s
3
6. Corey, E.J. and Noyori, R., Tetrahedron Lett., 1970,
(2H, SCH2C=), 5.88 q (1H, CH=, J = 7.0 Hz).
13C NMR spectrum, δC, ppm: 13.64 (CH3), 29.85,
33.07 (SCH2CH2S), 39.28 (SCH2C=), 126.11 (CH=),
127.52 (=CS). Mass spectrum: m/z 146 (Irel 100%)
[M]+. Found (isomer mixture), %: C 49.19; H 6.80;
S 44.12. C6H10S2. Calculated, %: C 49.27; H 6.89;
S 43.84. M 146.28.
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16.5 g (0.294 mol) of KOH, and 3.68 g (0.0294 mol)
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RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 54 No. 12 2018