Effect of chalcogenyl substituent on the course of allyl rearrangement at chalcogenation of 1,3-dichloropropene

Article abstract of DOI:10.1134/S1070428016050018

Formation of 1,3-dichalcogenylpropene at the treatment of 1,3-dichloropropene with organic dichalcogenides in a redox system hydrazine hydrate–KOH is governed by the possibility of an allyl rearrangement. In the presence of bases this rearrangement proceeds via carbanion partially stabilized by the chalcogenyl substituent. The effectivity of the stabilization and consequently the probability of the rearrangement varies in the series of substituents PhS > BnS > PhSe. In the stage of the direct nucleophilic substitution of chlorine the anion PhSe^?possesses the highest activity.

Full text of DOI:10.1134/S1070428016050018

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2016, Vol. 52, No. 5, pp. 615–623. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © E.P. Levanova, V.S. Nikonova, V.A. Grabel’nykh, N.V. Russavskaya, A.I. Albanov, I.B. Rozentsveig, N.A. Korchevin, 2016,
published in Zhurnal Organicheskoi Khimii, 2016, Vol. 52, No. 5, pp. 631–639.
Effect of Chalcogenyl Substituent on the Course of Allyl
Rearrangement at Chalcogenation of 1,3-Dichloropropene
E. P. Levanova, V. S. Nikonova, V. A. Grabel’nykh*, N. V. Russavskaya,
A. I. Albanov, I. B. Rozentsveig, and N. A. 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 February11, 2016
Abstract—Formation of 1,3-dichalcogenylpropene at the treatment of 1,3-dichloropropene with organic
dichalcogenides in a redox system hydrazine hydrate–KOH is governed by the possibility of an allyl
rearrangement. In the presence of bases this rearrangement proceeds via carbanion partially stabilized by the
chalcogenyl substituent. The effectivity of the stabilization and consequently the probability of the
rearrangement varies in the series of substituents PhS > BnS > PhSe. In the stage of the direct nucleophilic
substitution of chlorine the anion PhSe‒ possesses the highest activity.
DOI: 10.1134/S1070428016050018
Hetero-substituted allyl systems are important
reagents in organic synthesis [1]. With the use of allyl
chalcogenides the high temperature synthesis of
benzothiophene and its analogs was performed [2], the
possibility was studied of allyl rearrangement [3] and
of Claisen rearrangement [4] in the allyl phenyl
chalcogenide series.
1,3-bis(phenylsulfanyl)propene formed in 35–78%
yields [7].
1,3-Bisselanyl propene derivatives were obtained
with the use of difficultly available selanylallyl
alcohols and the corresponding selenols (yield 77–
82%), and also from selanylacetic aldehyde and Wittig
reagent (yield 60%) [8]. 1,3-Bis(phenylsulfanyl)-
propene was obtained in 43% yield by the reaction of
butyllithium with 2-methoxy-1,3-bis(phenylsulfanyl)-
propane [9]. 1,3-Bis(phenylsulfanyl)propene (yield
85%) and 1,3-bis(phenylselanyl)propene (yield 90%)
were obtained by the reaction of 1,3-dichloropropene
with thiophenol in the presence of KOH or with
diphenyl diselenide in the presence of rongalite and
KOH respectively [10]. In both cases the reaction was
carried out in highly basic medium with excess KOH.
Reaction products are formed as a result of successive
transformations, and the key stage is the allyl
rearrangement of the primarily formed product of
chlorine monosubstitution at the sp3-hybridized carbon
atom; the double bond shifts to the chalcogen atom.
This rearrangement proceeds evidently through an
intermediate formation of a carbanion whose stability
is governed by the influence of the contiguous
chalcogenyl groups [10]. This influence depends both
on the nature of the chalcogen atom and on the
The general preparation method of allyl
monochalcogenides is the reaction of chalcogen-
containing nucleophiles with allyl halides. In the
majority of these reactions the conditions may be
adjusted leading to high yields of target compounds.
Allyl derivatives with two chalcogenyl substituents
in the positions 1, 3 are far less understood, although
their synthetic potential in many instances may be
higher than that of monochalcogenides. A lithium
derivative of 1,3-bis(methylsulfanyl)propene plays the
role of a synthetic equivalent of a hypothetic acrolein
β-anion which may underlie the preparation of
versatile unsaturated structures [5]. Several approaches
were suggested for the synthesis of 1,3-bischalcogenyl
propene derivatives. 1,3-(Dibutylsulfanyl)- or 1,3-
(diphenylsulfanyl)propene were obtained in 15–20%
yields in reactions of 1,1-dichloroprop-2-ene with
sodium butanethiolate or sodium thiophenolate [6]. In
the reaction of enones with tris(phenylsulfanyl)borate
615

LEVANOVA et al.
616
electronic properties of the organic substituent bound
to it.
nucleophilic substitution of the allyl chlorine with the
formation of [(3-chloroprop-2-en-1-yl)chalcogenyl]ben-
zenes 3a–3d (а), ionization of compounds 3 leading to
carbanions А1 (b), allyl rearrangement in carbanions А1,
resulting in the formation of [(3-chloroprop-1-en-1-yl)-
chalcogenyl]benzenes 4 (c), fast replacement of the
chlorine in the allyl position of compounds 4 to give
(propene-1,3-diyldichalcogenanediyl)dibenzenes 5 (d)
(Scheme 2).
The allyl rearrangement in the series of allyl phenyl
chalcogenides resulting in the migration of the double
bond to the chalcogen atom under the same conditions
occurs with sulfide to 95% and with the corresponding
selenide only to 53% [3].
Reactions of chalcogenation of 2,3-dichloroprop-1-
ene [11] and 1,4-dichlorobut-2-yne [12] include
several stages, and some among them involve
carbanions. The structure of formed compounds
depends on the possibility of stabilization by a
chalcogenyl substituent of the adjacent carbanion site.
In keeping with Scheme 2 the possibility of
conversion 3→5 is governed by the occurrence of the
allyl rearrangement (stages b, c), which in its turn
depends on the rate of deprotonation of compounds 3
and on the stability of anion А1, whose structure may
be represented as a resonance hybrid of anion forms А2
and А3. The deprotonation rate of compound 3 depends
on the alkali concentration in the system (on the ratio
R2Y2–KOН) and on the reaction temperature.
In continuation of this research we studied the
chalcogenation of commercially available 1,3-
dichloropropene 1 with chalcogenolates 2a–2d which
were obtained by the reduction of organic dichalco-
genides Ph2Y2 and Bn2S2 in the system hydrazine
hydrate–KOН [13] (Scheme 1). The reduction
products without isolation were used in the subsequent
syntheses.
The selective formation of compound 3а from
thiolate 2а (allyl rearrangement is absent) occurs only
at 0°С (ratio Ph2S2–KOН 1 : 5, yield of compound 3а
82%). However already at 25–35°С thiolate 2а in the
reaction with 1,3-dichloropropene 1 (Ph2S2–KOН, 1 : 5)
forms a mixture of compounds 3а and 5а in a ratio 1 : 6
(yield of compound 5а 67%). At the same temperature
but at higher alkali concentration (Ph2S2–KOН, 1 : 10)
the reaction product is exclusively 1,3-bis(phe-
nylsulfanyl) propene derivative 5а (yield 63%). At the
ratio Ph2S2–KOН 1 : 5 the selective formation of
compound 5а (yield 62%) occurs at 60°С.
Scheme 1.
4RYK + N2 + 5H2O
2R2Y2 + N2H4 H2O + 4KOH
2a_2d
R = Ph, Y = S (а), Se (b), Te (c); R = Bn, Y = S (d).
In keeping with [10] and the presumed mechanism
of the allyl rearrangement [14] the reaction of 1,3-
dichloropropene
1
with chalcogenolates 2a–2d
At the use of reagents 2b–2d even at 25–35°С only
proceeds through several stages including the
the first stage of the reaction presented in Scheme 2
Scheme 2.
a
Cl
Cl
Cl
YR
RYK
+
_KCl
1
2a_2d
3a_3d
_ b
OH , _H2O
Cl
YR
Cl
YR
Cl
YR
_
_
_
_
H2O, _OH
A2
A3
A1
c
d
_
H2O, _OH
2a_d
Cl
YR
RY
YR
_
_KCl
OH , _H2O
4
5a_5c
R = Ph, Y = S (а), Se (b), Te (c); R = Bn, Y = S (d).
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EFFECT OF CHALCOGENYL SUBSTITUENT ON THE COURSE OF ALLYL
617
Scheme 3.
PhSK (2a)
2b
Cl
SPh
PhSe
SPh
3a
3b
_KCl
_KCl
a
1
25_35°C
PhSeK (2b)
4a
6
_KCl
3a
3b
4a
6
1
60°C, 9.5 h
PhSeK
_KCl
Cl
SePh
5b
4b
occurs with the formation compounds 3b–3d in 92, 68,
37% yields respectively. These results are well
consistent with the data of [11, 12], where it has been
demonstrated that the substituent PhS is the most
efficient stabilizer of the adjacent carbanion site.
intermediate compounds 3а and 3b underwent the allyl
rearrangement, and both isomerization products 4а and
4b reacted with selenolate 2b (Scheme 3).
In the reactions represented in Schemes 2, 3
commercial 1,3-dichloropropene 1 was used composed
of Е- and Z-isomers with a small excess of E-isomer
[E/Z (1.0–1.15) : 1.0, 1Н NMR data]. Compounds 3, 5,
and 6 also are composed of the corresponding Е- and
Z-isomers with the prevalence of the E-isomer [E/Z
(1.05–1.50) : 1.0], in agreement with the higher
thermodynamic stability of E-isomers. Compounds of
this type are not described in the literature. In [14]
from Е-1,3-dichloropropene was obtained only Е-
isomer of compound 3d isolated by column chromato-
graphy.
The increase in the temperature to 60°С makes it
possible to obtain from 1,3-dichloropropene 1 and
selenolate 2b 1,3-bis(phenylselanyl) propene deriva-
tive (76%), and from thiolate 2d, 1,3-bis(benzyl-
sulfanyl) propene derivative (68%). Diphenyl ditellu-
ride at this temperature affords a complex mixture of
substances.
At simultaneous bringing into the reaction with 1,3-
dichloropropene 1 two chalcogenolates 2а and 2b (25–
35°С) compounds 3b and 6 formed in the molar ratio
4.2 : 1.0 in 60 and 27% yields respectively calculated
with respect to the reacted Ph2Sе2 (1Н NMR data).
Apparently under the reaction conditions 1,3-
dichloropropene 1 in the stage а reacts predominantly
with phenylselenolate 2b and somewhat less
effectively with thiolate 2а. Yet the formed compounds
3а and 3b behave further differently: compound 3b
does not undergo the allyl rearrangement and remains
unchanged in the system, whereas sulfide 3а
isomerizes (stage b) into compound 4а that quickly
reacts prevailingly with PhSeK 2b (Scheme 3).
The selective formation of compounds 3a–3c
(Scheme 2) makes it possible to regard them as initial
compounds for the preparation of propene-1,3-
diylbischalcogenides 5 and 6. The independent
occurrence of these reactions confirms the assumed
mechanism of compounds 5 and 6 formation from 1,3-
dichloropropene 1 (Scheme 2), provides a possibility
to synthesize 1,3-dichalcogenyl propene derivatives
with diverse chalcogenyl substituents and to acquire
additional information on the effect of the substituent
nature on the course of the allyl rearrangement.
Compounds 3 with a single chalcogenyl fragment may
be used in the organic synthesis, for instance, for the
preparation of sulfonium methylides and a wide range
of unsaturated structures based on them [15].
At carrying out this concurrent reaction at 60°С
(9.5 h) also a mixture formed of two compounds:
bisselenide 5b (yield 27%) and mixed chalcogenide 6
(yield 32%). Obviously in these conditions the both
Scheme 4.
NH2
PhCH2Cl, N2H4 H2O_KOH
_CO2, _NH3, _KCl
_
Cl
S
+
Cl
1 + S=C(NH2)2
3d
NH2
7
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 5 2016

LEVANOVA et al.
618
Compound 3с formed with the smallest yield
apparently because of the well-known instability of
organotellurium compounds [16].
dichloromethane and ether. Selenolate 2b present in
the water-hydrazine layer at methylation formed sele-
noanisole 8 (Scheme 5), the yield of which was used to
calculate the quantity of PhSeK unreacted with
chlorosulfide 3а.
Since benzylsulfanyl derivative of chloropropene
3d is also isolated in a low yield (68%), and its Е-
isomer is obtained from phenylmethanethiol, Е-1,3-
dichloropropene, and trimethylamine in ether (25°С,
12 h) in 52% yield [15], we have developed an
alternative method of preparation of compound 3d
using isothiouronium salts with organic residue
sensitive to the action of bases [17].
Scheme 5.
PhSeCH3
2b + CH3I
_KI
8
Chloroselenide 3b at 25–35°C did not react with
Ph2S2, and at 60°C (Ph2S2–KOH, 1 : 5, 10 h) it formed
compound 6 in 72% yield (E/Z 1.3 : 1.0). In keeping
with Scheme 2 the reaction product should be com-
pound 9, yet it was not found in the reaction mixture.
Probably its formation along Scheme 3 is accompanied
with allyl rearrangement proceeding through carbanion
B stabilized with adjacent moiety PhS (Scheme 6). The
reverse rearrangement 6→9 is less probable since
carbanion C arising from compound 6 is located near
the group PhSe which stabilizes the anion site less
efficiently than the PhS group.
Isothiouronium salt 7 prepared from 1,3-dichlo-
ropropene 1 and thiourea was treated with benzyl
chloride gradually adding the basic redox mixture
N2H4·H2O–KOH (Scheme 4). By this procedure
compound 3d was obtained in 87% yield.
In reaction of chlorosulfide 3а with Ph2Se2 (25–35°C,
Ph2Se2–KOН, 1 : 5, 5 h) compound 6 was obtained,
yet the conversion of initial 3а was only 47%, and the
yield of mixed chalcogenide 6 was 74% (calculated
with respect to reacted Ph2Se2) with a significant
prevalence of Е-isomer (E/Z 11.6 : 1.0). The increase
in the temperature of the reaction between chlorosul-
fide 3а and selenolate 2b to 60°C (Ph2Se2–KOН, 1 : 5,
5 h) resulted in the formation of compound 6 in 81%
yield (E/Z 1.9 : 1.0). At increased quantity of KOH
(Ph2Se2–KOH 1 : 10) at 10–20°C (4 h) the conversion
of compounds 3 (50%) and the yield of compound 6
(81% calculated with respect to reacted Ph2Se2)
somewhat increased. The ratio of Е- and Z-isomers of
compound 6 under these conditions was 4.3 : 1.0. The
conversion of Ph2Se2 was estimated by treating with
methyl iodide the water-hydrazine layer remaining
after extraction of compounds 3а and 6 with
In the reaction of chloroselenide 3b with thiolate 2d
(60°C, Bn2S2–KOH, 1 : 10, 10 h) the main reaction
product (yield 63%) was mixed chalcogenide 10
(Scheme 6), whose structure was well consistent with
the general Scheme 2 of the formation of compound 5.
Compound 10 was obtained in 22% yield in
simultaneous reaction of Ph2Se2 and Bn2S2 with 1,3-
dichloropropene 1 [60°C, 10 h, Ph2Se2–Bn2S2, 1 : 1,
(Ph2S2 + Bn2S2)–KOH, 1 : 5]. The main reaction
product was bisselenide 5b (yield 45 %) that showed
the higher reactivity of PhSe– anions compared with
BnS– anions.
Scheme 6.
N2H4 H2O_KOH
2a
Cl
SePh
PhS
SePh
PhS
3b
_KCl
4b
9
_
_
OH
H2O
PhS
SePh
PhS
SePh
SBn
SePh
OH
_H2O
_
_
_
_OH
_H2O
C
B
6
BnSK
_KCl
PhSe
10, E/Z 1.3 : 1.0
3b
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 5 2016

EFFECT OF CHALCOGENYL SUBSTITUENT ON THE COURSE OF ALLYL
619
Scheme 7.
_
OH , _H2O
PhS
SBn
PhS
SBn
3a + 2d
_
11, E/Z 1.1 : 1.0
_
H2O, _OH
PhS
SBn
PhS
SBn
_
12, E/Z 1.7 : 1.0
In analogous conditions chlorosulfide 3а with
thiolate 2d afforded a mixture of two compounds: that
expected in conformity to Scheme 2 [3-(benzyl-
sulfanyl)prop-1-en-1-yl]sulfanylbenzene 11 and the
product of its allyl rearrangement 12 in ~1 : 1 ratio;
each compound was a mixture of E- and Z-isomers,
1.1 : 1.0 (11), 1.7 : 1.0 (12). The overall yield of the
mixture of compounds 11 and 12 was 76%. The
possibility of the partial isomerization 11→12 is due to
nearly equal stabilization of the carbanion site with the
groups PhS and BnS (Scheme 7), yet in the reaction
with 1,4-dichlorobut-2-yne [13] more efficient
stabilization of carbanion with PhS is observed.
13С), Me2Se (77Se), (CH3)2Te (125Tе). Mass spectra
were measured on an GC-MS instrument Shimadzu
GCMS–QP5050A (column SPB-5, 60000 × 0.25 mm),
quadrupole mass analyzer, electron impact, 70 eV,
temperature of ion source 190°С, range of detected
masses 34–650 Da.
The monitoring of reaction progress and the
analysis of liquid substances was carried out on a chro-
matograph LKhM 80-MD-2 (column 2000 × 3 mm,
liquid phase DC-550, 5% on carrier Chromaton N-
AW-HMDS, linear programming of temperature at the
heating rate 12 deg/min, carrier gas helium).
1,3-Dichloropropene 1 was distilled prior to use.
Due to the considerable difference in boiling points of
isomers of compound 1 [112°С (E), 104.3°С (Z)] [18]
in different distillation conditions fractions were
obtained with various isomer ratio (1Н NMR data) with
the prevalence of Е-isomer.
The attempt to prepare compounds 11 and 12 by the
simultaneous reaction of Ph2S2 and Bn2S2 [60°C, 9 h,
(Ph2S2 + Bn2S2)–KOH, 1 : 5] resulted in the formation
of a complex mixture of substances where compounds
1
(Е,Z)-11 and (Е,Z)-12 were detected by Н NMR
spectroscopy. In the reaction of chlorosulfide 3d with
thiolate 2а (Ph2S2–KOH, 1 : 10, 60°C, 10 h) a complex
mixture of nonidentifiable substances was obtained.
Reactions of diphenyl and dibenzyl dichal-
cogenides R2Y2 with 1,3-dichloropropene. General
procedure. To a solution of a calculated quantity of
potassium hydroxide in hydrazine hydrate
corresponding to the necessary ratio R2Y2–KOH was
added R2Y2. The obtained mixture was heated at
stirring for 2 h at 80–85°С, then it was cooled to
desired temperature (0, 25, or 60°С) and 1,3-
dichloropropene 1 was added dropwise. The reaction
mixture was stirred at the temperature of the
experiment for 4–21 h. The reaction products were
extracted with СH2Cl2 (2 × 30–50 mL) and ethyl ether
(2 × 30–50 mL). The combined extracts were dried
with MgSO4. The solvent was distilled off, the residue
was studied by NMR, IR, and GC-MS spectroscopy,
and subjected to further workup.
Thus the reactions of 1,3-dichloropropene with
diphenyl and dibenzyl dichalcogenides in the system
hydrazine hydrate–KOН provide versatile unsaturated
organic chalcogenides. The key stage of compounds
formation containing two chalcogen atoms is the allyl
rearrangement that most efficiently occurs in the case
of PhS substituent, then BnS, and PhSe. Among the
studied anions the highest reactivity is demonstrated
by PhSe‒.
EXPERIMENTAL
IR spectra were recorded on a spectrophotometer
1
Bruker IFS-25 from thin films. Н, 13С, 77Se, 125Tе
NMR spectra were registered on a spectrometer Bruker
DPX-400 (400.13, 100.62, 76.31, and 126.2 MHz
respectively) in CDCl3, internal reference TMS (1Н,
Compounds 3a, 3b, 3d, 5a, 5b, 5d, 6, and 10 were
obtained as mixtures of E- and Z-isomers. The other com-
pounds were identified by 1Н, 13С, 77Se, and 125Tе NMR
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 5 2016

LEVANOVA et al.
620
spectroscopy in mixtures with the other reaction pro-
ducts. The attempts at vacuum distillation (1–2 mmHg)
resulted in a fast decomposition of the mixtures
components.
7.7 Hz), 5.97 d (1Н, =СHCl, Jcis 7.1 Hz), 7.23 m (3Н,
Hp,m, С6Н5), 7.46, 7.50 m (2Н, Нo). 13С NMR spec-
trum, δ, ppm: 22.99 (CH2Sе, JСSe 59.7 Hz), 119.30
1
(=СHCl), 127.38 (Cp), 128.18 (=СНCH2), 129.07 (Co),
133.23 (Сi), 133.54 (Cm). 77Se NMR spectrum, δ, ppm:
340.7. At GC-MS study two peaks are observed on the
chromatogram that in the mass spectra correspond to
clusters of molecular ions, m/z 232 [M]+ (35Cl, 80Se).
Found, %: C 46.24; H 3.99; Cl 14.86; Sе 33.65.
C9H9ClSе. Calculated, %: C 46.68; H 3.92; Cl 15.31;
Sе 34.09.
Anions 2а and/or 2b in water-hydrazine layer
conserved after reaction products extraction were
determined by converting them in thioanisole or
selenoanisole by treating with methyl iodide [19].
[(3-Chloroprop-2-en-1-yl)sulfanyl]benzene (3а)
was obtained from 8 g (0.037 mol) of Ph2S2, 10.36 g
(0.185 mol) of KOН, 8.2 g (0.074 mol) dichloropro-
pene 1 in 50 mL of hydrazine hydrate (from 0 to –3°С,
10 h). Yield 82% (Е/Z 1.15 : 1.0). Colorless liquid, bp
98–100°С (2 mmHg) {132°С (3 mmHg) [6], 79–80°С
(1 mmHg) [20]}. IR spectrum, ν, cm–1: 1624 (С=С).
[(3-Chloroprop-2-en-1-yl)tellanyl]benzene (3с). In
the reaction of 2.0 g (0.0049 mol) of Ph2Tе2 with 1.08 g
(0.01 mol) of dichloropropene 1, 1.37 g (0.0244 mol)
of KOH in 6 mL of hydrazine hydrate (2.5 h at 25°С, 2 h
at 30–35°С) we obtained 2.38 g of dark red liquid con-
1
taining according to H and 125Tе NMR data Ph2Tе2
1
Е-Isomer. H NMR spectrum, δ, ppm: 3.45 m (2H,
and compound 3c in a molar ratio 1 : 1. Yield 38%
with respect to 1,3-dichloropropene 1 brought into
reaction. According to NMR data a mixture of E- and
Z-isomers, 2.5 : 1.0, yet in the mixture with diphenyl
ditelluride it was impossible to identify the isomers. IR
spectrum, ν, cm–1: 1617 (С=С) (the absorption bands
of nearly the same intensity were present at 1656 and
СН2S), 5.93 m (2H, CH=CH), 7.19–7.35 m (5H,
C6H5). 13С NMR spectrum, δ, ppm: 34.86 (CH2S),
120.36 (=СHCl), 126.96 (Cp), 128.97 (=СНCH2),
129.00 (Co), 130.85 (Cm), 134.82 (Сi).
Z-Isomer. 1H NMR spectrum, δ, ppm: 3.68 d.d (2H,
SСН2, 2J 7.0, 4J 1.2 Hz), 5.83 d.t (1H, =CHCH2, 3J 7.0,
4
1
1680 cm–1, which were not identified). H NMR spec-
Jcis 7.0 Hz), 6.06 d.t (1H, =CHСl, Jcis 7.0, J 1.2 Hz),
7.19–7.35 m (5Н, С6Н5). Mass spectrum, m/z: 186 [M]+
(37Cl) and 184 [M]+ (37Cl). Found, %: C 58.78; H 4.93;
Cl 19.06; S 17.40. C9H9ClS. Calculated, %: C 58.53; H
4.91; Cl 19.20; S 17.39.
trum, δ, ppm: 3.44 m, 3.68 m (СН2Tе), 5.83 m, 5.99 m
(СН=), 7.11–7.73 m (С6Н5). 13С NMR spectrum, δ,
ppm: 2.88, 6.96 (СН2Tе), 117.61, 118.85 (=СHCl),
128.02, 129.21 (Cm), 128.25, 129.73 (Cp), 131.58,
139.67 (=СНCH2), 137.63, 139.37 (Co), 129.73,
139.77 (Сi). 125Te NMR spectrum, δ, ppm: 421.77
(Ph2Te2) [21], 596.29, 597.64 (intensity ratio 2.5 : 1).
[(3-Chloroprop-2-en-1-yl)selanyl]benzene (3b)
was obtained from 2.2 g (0.007 mol) of Ph2Sе2, 1.98 g
(0.035 mol) of KOН in 9 mL of hydrazine hydrate and
0.782 g (0.007 mol) of 1,3-dichloropropene 1 at 25°С
(2.5 h) and 30–35°С (2 h). Yield 92%, light-yellow
liquid. Conversion of Ph2Sе2 was estimated by the
formation of selenoanisole 8 (0.9 g), 63%. Yield of
compound 3b calculated with respect to reacted Ph2Sе2
87%, Е/Z 1.06 : 1.0. IR spectrum, ν, cm1: 1620 (С=С).
At 25°С and the ratio Ph2Sе2–1 1 : 2 yield of
compound 3b 91% at a complete conversion of Ph2Sе2.
We failed to obtain the mass spectrum of compound
3с because of its complete decomposition in the
chromatographic column of mass spectrometer.
{[(3-Chloroprop-2-en-1-yl)sulfanyl]methyl}ben-
zene (3d). a. was obtained from 6.0 g (0.0244 mol) of
Bn2S2, 6.84 g (0.122 mol) of KOH, 30 mL of hydra-
zine hydrate, and 5.42 g (0.0488 mol) of dichloro-
propene 1 (2.5 h at 25°С and 2 h at 30–35°С). Yield
68%, bp 114–116°С (2 mmHg). Colorless liquid,
mixture of Е- and Z-isomers, 1.1 : 1.0. IR spectrum, ν,
cm–1: 1624 s, 1602 w (С=С).
1
Е-Isomer. H NMR spectrum, δ, ppm: 3.39 d (2H,
СН2Sе, 3J 8.1 Hz), 5.76 d (1H, =CHСl, Jtrans 13.2 Hz),
3
5.99 d.t (1H, =CHСН2, J 8.1, Jtrans 13.2 Hz), 7.23–
13
7.50 m (5H, C6H5). С NMR spectrum, δ, ppm: 27.47
Е-isomer. 1H NMR spectrum, δ, ppm: 2.91 d.d (2H,
1
(CH2Sе, JСSe 60.0 Hz), 120.05 (=СHCl), 127.71 (Cp),
SСН2С=, 3J 7.3, 4J 0.9 Hz), 3.60 s (2H, SCH2Ph), 5.84
129.00 (Co), 129.80 (=СНCH2), 131.79 (Сi), 134.19
(Cm). 77Se NMR spectrum, δ, ppm: 346.3.
3
d.t (1Н, =СНСН2, J 7.3, Jtrans 13.2 Hz), 5.92 d.t (1Н,
=СНСl, Jtrans 13.2, 4J 0.9 Hz), 7.08–7.29 m (5H, C6H5)
(cf. [9]). 13С NMR spectrum, δ, ppm: 30.88
(SСН2СH=), 35.09 (SCH2Ph), 119.73 (=СНСl), 127.06
1
Z-Isomer. H NMR spectrum, δ, ppm: 3.64 d (2H,
3
3
СН2Se, J 7.7 Hz), 5.91 d.t (1H, =CHCH2, Jcis 7.1, J
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 5 2016

EFFECT OF CHALCOGENYL SUBSTITUENT ON THE COURSE OF ALLYL
621
(Cp), 128.51 (Co), 128.90 (Cm), 129.64 (=СНCH2),
137.69 (Сi).
(Propene-1,3-diyldiselandiyl)dibenzene (5b) was
obtained from 2.2 g (0.007 mol) of Ph2Sе2, 1.98 g
(0.035 mol) of KOH, 10 mL of hydrazine hydrate, and
0.78 g (0.007 mol) of 1,3-dichloropropene 1 (60°С,
19 h). After evaporation of solvents yield 76%, mixture
of Е- and Z-isomers, 1.25 : 1.0, yellow liquid, bp 120°С
(0.12 mmHg) [8]. At the residual pressure 1–2 mmHg
the substance suffers fast decomposition. IR spectrum,
ν, cm–1: 1599 w, 1578 s (С=С).
Z-Isomer. 1H NMR spectrum, δ, ppm: 3.19 d.d (2Н,
SCH2С=, 3J 7.5, 4J 1.2 Hz), 3.64 s (2Н, SCH2Ph), 5.76
3
d.t (1H, =CHCH2, J 7.5, Jcis 7.2 Hz), 6.06 d.t (1Н,
4
=СHCl, Jcis 7.2, J 1.2 Hz), 7.08–7.29 m (5H, C6H5).
13С NMR spectrum, δ, ppm: 27.59 (SСН2СН=), 35.75
(SCH2Ph), 120.02 (=СНСl), 126.99 (Cp), 128.30
(=СНCH2), 128.42 (Co), 128.90 (Cm), 138.02 (Сi). In
mass spectra of each isomer to the molecular ion
correspond values of m/z 198 [M]+ (35Cl), 200 [M]+
(37Cl). Found, %: C 60.88; H 5.48; Cl 17.52; S 15.64.
C10H11ClS. Calculated, %: C 60.44; H 5.58; Cl 17.84;
S 16.13.
1
Е-Isomer. H NMR spectrum, δ, ppm: 3.50 d (2Н,
CH2Se, 3J 7.8 Hz), 6.06 d.t (1Н, =СНСН2, 3J 7.8, Jtrans
15.0 Hz), 6.23 d (1Н, =СНSе, Jtrans 15.0 Hz), 7.17–
7.48 m (10Н, С6Н5) [8, 10]. 13С NMR spectrum, δ,
1
ppm: 30.96 (SeCH2, JCSe 58.9 Hz), 120.14 (=CHSe).
The rest of signals were not attributed to E- and Z-
isomers. Se NMR spectrum, δ, ppm: 345.5 (SeCH2),
376.2 (SeCH=).
b. From 1.25 g (0.0067 mol) of isothiouronium salt
7 (prepared by procedure [22]), 0.85 g (0.0067 mol) of
benzyl chloride, 0.75 g (0.0134 mol) of KOH, and 3 mL
of hydrazine hydrate under the conditions described in
[17]. Yield 87% (Е/Z ~1 : 1). The spectral characteris-
tics and elemental analysis data totally coincide with
those mentioned above.
77
1
Z-Isomer. H NMR spectrum, δ, ppm: 3.67 d (2Н,
3
3
CH2Se, J 7.8 Hz), 6.19 d.t (1Н, =СНСН2, Jcis 8.9, J
7.8 Hz), 6.46 d (1Н, =СНSе, Jcis 8.9 Hz), 7.17–7.48 m
(10Н, С6Н5). 13С NMR spectrum, δ, ppm: 27.44 (SeCH2,
1JCSe 58.5 Hz), 123.66 (=CHSe). Se NMR spectrum,
77
(Propene-1,3-diyldisulfandiyl)dibenzene (5а) was
obtained from 4.0 g (0.0180 mol) of Ph2S2, 10.27 g
(0.183 mol) of KOH, 2.0 g (0.0180 mol) of dichloro-
propene 1 in 45 mL of hydrazine hydrate. Yield 63%,
bp 177–179°С (2 mmHg) {192–198°С (3.2 mmHg)
[9]}, Е/Z 1.5 : 1.0. IR spectrum, ν, cm–1: 1606 w, 1583
s (C=C).
δ, ppm: 327.1 (SeCH=), 343.8 (SeCH2).
[Propene-1,3-diyl(bissulfandiylmethylene)]di-
benzene (5с) was obtained from 2.46 g (0.01 mol) of
Bn2S2, 2.81 g (0.05 mol) of KOH, 12 mL of hydrazine
hydrate, and 1.11 g (0.01 mol) of dichloropropene 1
(60°С, 21 h). Mixture of Е- and Z-isomers, 0.9 : 1.0,
yield 58%. IR spectrum, ν, cm–1: 1602 (С=С).
Е-Isomer. 1H NMR spectrum, δ, ppm: 3.54 d.d (2Н,
1
SCH2, 3J 7.2, 4J 0.9 Hz), 5.86 d.t (1Н, =СНСН2, 3J 7.2,
Е-Isomer. H NMR spectrum, δ, ppm: 2.96 d (2Н,
4
3
Jtrans 14.8 Hz), 6.11 d.t (1Н, =СНSPh, Jtrans 14.8, J
=СНCH2S, J 7.6 Hz), 3.50 s (2Н, SCH2Ph), 3.82 s
3
0.9 Hz), 7.05–7.36 m (10Н, С6Н5). 13С NMR spectrum,
δ, ppm: 36.80 (SCH2), 126.39, 126.61** (Сp), 127.72,
128.89** (Сi), 130.90, 129.07** (Co), 128.83, 129.00**
(Cm), 128.81 (=CHCH2), 128.89 (=CHS).
(2Н, SCH2Ph), 5.52 d.t (1Н, =СНСН2S, J 7.6, Jtrans
14.9 Hz), 5.94 d (1Н, =СНS, Jtrans 14.9 Hz), 7.13–7.28
m (10Н, С6Н5). The signals in 13С NMR spectrum of the
isomers mixture were not unambiguously identified.
1
1
Z-Isomer, H NMR spectrum: 3.73 d.d (2Н, SCH2,
Z-Isomer. H NMR spectrum, δ, ppm: 3.12 d (2Н,
3J 7.5, J 0.7 Hz), 5.83 d.t (1Н, =СНСН2, J 7.5, Jcis
9.2 Hz), 6.25 d.t (1Н, =СНSPh, Jcis 9.2, J 0.7 Hz),
=СНCH2S, J 7.5 Hz), 3.55 s (2Н, SCH2Ph), 3.82 s
(2Н, SCH2Ph), 5.57 d.t (1Н, =СНСН2S, J 7.5, Jcis
4
3
3
4
3
7.05–7.36 m (10Н, С6Н5). 13С NMR spectrum, δ, ppm:
31.95 (SCH2), 125.53, 126.08** (Сp), 128.10, 129.62**
(Cm), 128.72, 129.03** (Co), 130.70, 127.51** (Ci),
126.48 (=CHCH2), 129.01 (=CHS). In the mass spectra
of both isomers molecular ion is observed, m/z 258.
Found, %: C 70.09; H 5.44; S 24.81. C15H14S2. Calcu-
lated, %: C 69.72; H 5.46; S 24.81.
9.4 Hz), 6.05 d (1Н, =СНS, Jcis 9.4 Hz), 7.13–7.28 m
(10Н, С6Н5). Found, %: C 70.83; H 6.18; S 22.58.
C17H18S2. Calculated, %: C 71.28; H 6.33; S 22.38.
[3-(Phenylselanyl)prop-1-en-1-ylsulfanyl]ben-
zene (6) a. was obtained from 1.18 g (0.0064 mol) of
compound 3а, 1.0 g (0.0032 mol) Ph2Se2, 1.8 g
(0.032 mol) of KOH, (Ph2Se2–KOH 1 : 10) in 8 mL of
hydrazine hydrate (10–20°С, 4 h), mixture of Е- and Z-
isomers, 4.3 : 1.0. Conversion of compound 3а 60%,
conversion of Ph2Se2 47%. Yield 78% calculated with
**
First the chemical shift of PhS at CH2 is given, then of PhS at
the double bond.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 5 2016

LEVANOVA et al.
622
respect to the reacted chloride 3а, 98% calculated with
respect to the reacted Ph2Se2. In 2.5 h at 20°С and 2 h
at 30–35°С yield 74% calculated with respect to the
reacted Ph2Se2. Conversion of Ph2Se2 68%, conversion
of chloride 3а 47%. Virtually complete conversion of
compound 3а was obtained at 60°С in 5 h, yield 81%
calculated with respect to the Ph2Se2 taken in the
reaction, the ratio of Е- and Z-isomers 1.9 : 1.0).
Isomers characterized in the mixture with unreacted
chloride 3а. IR spectrum, ν, cm–1: 1601 w, 1580 s
(С=С). Found, %: C 59.08; H 4.70; Sе 25.96. C15H14SSe.
Calculated, %: C 59.01; H 4.62; Se 25.86.
~1.0 : 1.0) (yield 27%). Spectral characteristics of com-
pounds 6 and 5b are fully identical to those mentioned
above.
[3-(Benzylsulfanyl)prop-1-en-1-ylselanyl]ben-
zene (10) а. was obtained from 1.1 g (0.0048 mol) of
compound 3b and 0.59 g (0.0024 mol) of dibenzyl
disulfide in 6 mL of hydrazine hydrate, and 1.34 g
(0.024 mol) of KOH (60°С, 10 h). Yield 80% (E/Z
1.3 : 1.0). Light-yellow liquid. IR spectrum, ν, cm–1:
1600 m, 1579 m (С=С). Found, %: C 60.00; H 5.14; S
10.47; Sе 24.29. C16H16SSe. Calculated, %: C 60.18; H
5.05; S 10.04; Se 24.73.
1
1
Е-Isomer. H NMR spectrum, δ, ppm: 3.51 d (2Н,
Е-Isomer. H NMR spectrum, δ, ppm: 3.45 d (2Н,
3
3
3
CH2SePh, J 3.4 Hz), 5.93 d.t (1Н, =СНСН2, J 3.4,
=СCH2S, J 7.6 Hz), 3.72 s (2Н, SCH2Ph), 5.67 d.t
3
J
trans 14.4 Hz), 5.91 d (1Н, =СНS, Jtrans 14.4 Hz), 7.00–
(1Н, =СНСН2, J 7.6, Jtrans 14.8 Hz), 5.80 d (1Н,
7.46 m (10Н, С6Н5). 13С NMR spectrum, δ, ppm:
=СНSe, Jtrans 14.8 Hz), 7.16–7.461 m (10Н, С6Н5). 13С
NMR spectrum, δ, ppm: 25.56 (SCH2CH=), 37.94
(SCH2Ph), 125.94 (=CHCH2), 127.08 (=CHSe), 127.20,
126.95 (Cp), 128.88, 128.79 (Cm), 133.15, 128.54 (Co),
132.64, 137.63 (Ci). 77Se NMR spectrum, δ, ppm:
340.2.
1
20.98 (CH2Se, JCSe 58.9 Hz), the rest of signals were
not unambiguously identified. Se NMR spectrum, δ,
77
ppm: 348.8.
1
Z-Isomer. H NMR spectrum, δ, ppm: 3.65 d (2Н,
3
3
CH2Se, J 6.8 Hz), 5.92 d (1Н, =СНСН2Se, J 6.8, Jcis
7.9 Hz), 6.15 d.t (1Н, =СНS, 3J 6.8, Jcis 7.9 Hz), 7.00–
7.46 m (10Н, С6Н5). 13С NMR spectrum, δ, ppm:
1
Z-Isomer. H NMR spectrum, δ, ppm: 3.60 d (2Н,
3
=СHCH2S, J 8.1 Hz), 3.74 s (2Н, SCH2Ph), 5.69 d.t
1
77
(1Н, =СНСН2, 3J 8.1, Jcis 9.3 Hz), 5.93 d (1Н, =СНSe,
Jcis 9.3 Hz), 7.16–7.47 m (10Н, С6Н5). 13С NMR
spectrum, δ, ppm: 30.32 (SCH2CH=), 37.09 (SCH2Ph),
125.13 (=CHCH2), 125.93 (=CHSe), 127.29, 127.15
(Cp), 128.72, 128.51 (Cm), 133.91, 128.90 (Co), 132.87,
137.22 (Ci). 77Se NMR spectrum, δ, ppm: 347.2.
25.27 (SeCH2, JCSe 58.9 Hz). Se NMR spectrum, δ,
ppm: 345.5.
b. The compound was obtained from 1.5 g
(0.0065 mol) of compound 3b, 0.71 g (0.00325 mol) of
Ph2S2 in the presence of 1.82 g (0.0325 mol) of KOH
and 8 mL of hydrazine hydrate. Yield 72%, mixture of
E- and Z-isomers, 1.3 : 1.0. Spectral characteristics are
fully identical to those mentioned above.
b. The compound was obtained from 1.08 g
(0.0027 mol) of compound 3с and 0.84 g (0.0027 mol)
of Ph2Se2 in the presence of 1.51 g (0.027 mol) of
KOH and 7 mL of hydrazine hydrate (60°С, 10 h).
Yield 65%, the ratio of E- and Z-isomers 1.3 : 1.0.
Spectral characteristics are fully identical to those
mentioned above.
c. The compound was obtained from 1.42 g
(0.0128 mol) of compounds 1, 1.4 g (0.0064 mol) of
Ph2S2, and 2.0 g (0.0064 mol) of Ph2Se2 in 2.5 h at 25°С
and 2 h at 30–35°С. Dichalcogenides were separately
reduced in the system of 1.8 g (0.032 mol) of KOH
and 8 mL of hydrazine hydrate, the solutions were
combined and brought into the reaction with dichlo-
ropropene 1. Conversion of Ph2Se2 87%, conversion of
Ph2S2 66%. Yield of compound 6 27% (calculated with
respect to reacted Ph2Se2); compound 3b was obtained
in 60% yield (calculated with respect to reacted
Ph2Se2). Spectral characteristics of compounds 6 and
3b are fully identical to those mentioned above.
[3-(Benzylsulfanyl)prop-1-en-1-ylsulfanyl]ben-
zene (11) and [3-(benzylsulfanyl)prop-2-en-1-ylsul-
fanyl]benzene (12) (1 : 1) were obtained in an overall
yield 76% from 1.2 g (0.0065 mol) of compound 3а,
0.8 g (0.00325 mol) of Bn2S2, 1.82 g (0.0325 mol) of
KOH in 8 mL of hydrazine hydrate (60°С, 9.5 h). The
ratios of E- and Z-isomers are given in the main text.
Е-Isomer of compound 11. 1H NMR spectrum, δ, ppm:
3
4
3.06 d.d (2Н, =СНСН2, J 7.5, J 1.1 Hz), 3.75 s (2Н,
At 60°С (9.5 h) at virtually complete conversion of
Ph2Se2 (97%) a mixture was formed of compound 6
(E/Z ~1.0 : 1.0) (yield 32% with respect to dichloro-
propene 1 taken in the reaction) and compound 5b (E/Z
3
CH2Ph), 5.79 d.t (1Н, =СНСН2, J 7.5, Jtrans 14.9 Hz),
4
6.18 d.t (1Н, =СНS, J 1.1, Jtrans 14.9 Hz), 7.14–7.28
m (10Н, С6Н5).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 52 No. 5 2016

EFFECT OF CHALCOGENYL SUBSTITUENT ON THE COURSE OF ALLYL
623
1
10. Reich, H.J., Clark, M.C., and Willis, W.W. Jr., J. Org.
Chem., 1982, vol. 47, p. 1618.
Z-Isomer of compound 11. H NMR spectrum, δ,
ppm: 3.26 d.d (2Н, =СНСН2, 3J 7.5, 4J 1.0 Hz), 3.70 s
3
11. Levanova, E.P., Vakhrina, V.S., Grabel’nykh, V.A.,
Rozentsveig, I.B., Russavskaya, N.V., Albanov, A.I.,
and Korchevin, N.A., Russ. Chem. Bull., 2014, vol. 63,
p. 1722.
(2Н, CH2Ph), 5.80 d.t (1Н, =СНСН2, J 7.5, Jcis
9.2 Hz), 6.31 d.t (1Н, =СНS, Jcis 9.2, 4J 1.0 Hz).
1
Е-Isomer of compound 12. H NMR spectrum, δ,
ppm: 3.47 d.d (2Н, =СНСН2, 3J 7.2, 4J 1.1 Hz), 3.65 s
12. Levanova, E.P., Vakhrina, V.S., Grabel’nykh, V.A.,
Rozentsveig, I.B., Russavskaya, N.V., Albanov, A.I.,
Klyba, L.V., and Korchevina, N.A., Izv. Akad. Nauk, Ser.
Khim., 2015, vol. 64, p. 2083.
3
(2Н, SCH2Ph), 5.60 d.t (1Н, =СНСН2, J 7.2, Jtrans
15.0 Hz), 5.97 d.t (1Н, =СНS, Jtrans 15.0, 4J 1.1 Hz).
1
Z-Isomer of compound 12. H NMR spectrum, δ,
ppm: 3.59 d.d (2Н, =СНСН2, 3J 7.3, 4J 1.1 Hz), 3.77 s
13. 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, p. 2473.
3
(2Н, SCH2Ph), 5.60 d.t (1Н, =СНСН2, J 7.3, Jcis
9.3 Hz), 6.01 d.t (1Н, =СНS, Jcis 9.3, J 1.1 Hz). 13С
4
14. Borovlev, I.V., Organicheskaya khimiya: terminy i
osnovnye reaktsii (Organic Chemistry: Terminology and
the Basic Reactions), Moscow: BINOM. Laboratoriya
Znanii, 2010.
NMR spectrum of the mixture was impossible to
unambiguously interpret.
The main results were obtained on the equipment of
the Baikal analytic center of joint usage of the Siberian
Branch, Russian Academy of Sciences.
15. Nishimura, T., Zhang, C., Maeda, Y., Shirai, N., Ike-
da, Sh., and Sato, Y., Chem. Pharm. Bull., 1999, vol. 47,
p. 267.
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