Reactions of 2,3-dichloro-1-propene with sulfur and tellurium in the system hydrazine hydrate-KOH

Article abstract of DOI:10.1134/S1070363209060103

2,3-Dichloro-1-propene reacts with sulfur dissolved in the system hydrazine hydrate-KOH (with formation of K₂S₂ or K₂S) to afford bis(2-chloro-1-propene-3-yl)sulfide as the main product in both cases. Under similar conditions tellurium induces β-elimination of both chlorine atoms resulting in the formation of allene and complete regeneration of tellurium metal.

Full text of DOI:10.1134/S1070363209060103

ISSN 1070-3632, Russian Journal of General Chemistry, 2009, Vol. 79, No. 6, pp. 1097–1101. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © E.P. Levanova, V.A. Grabel’nykh, N.V. Russavskaya, L.V. Klyba, E.R. Zhanchipova, A.I. Albanov, О.А. Tarasova, N.А. Korchevin,
2009, published in Zhurnal Obshchei Khimii, 2009, Vol. 79, No. 6, pp. 925–929.
Reactions of 2,3-Dichloro-1-propene with Sulfur
and Tellurium in the System Hydrazine Hydrate–KOH
E. P. Levanova, V. A. Grabel’nykh, N. V. Russavskaya, L. V. Klyba,
E. R. Zhanchipova, A. I. Albanov, О. А. Tarasova, 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 December 8, 2008
Abstract—2,3-Dichloro-1-propene reacts with sulfur dissolved in the system hydrazine hydrate–KOH (with
formation of K2S2 or K2S) to afford bis(2-chloro-1-propene-3-yl)sulfide as the main product in both cases.
Under similar conditions tellurium induces β-elimination of both chlorine atoms resulting in the formation of
allene and complete regeneration of tellurium metal.
DOI: 10.1134/S1070363209060103
Reactions of organic dihalides with the alkali metal
polychalcogenides M2Yn (M = Na, K; Y = S, Se, Te;
n = 1–4) is a convenient preparative method for
synthesis of the polychalcogenide oligomers and
polymers. The so prepared polysulfide oligomers (Y =
S) are widely used as hermetics and produced in
industrial scale [1]. Selenium- and tellurium-contain-
ing oligomers attract the attention of researchers for
the design of promising electrotechnical materials [2].
Low-molecular derivatives prepared from dihalides
with participation of the alkali metal chalcogenolates
RYM (M = Na, K; Y = S, Se, Te) are effective
polydentate ligands for complex formation, in
particular with the heavy metal ions [3].
attached to the double bond [6]. In the latter case, the
formation of diphenylacetylene was observed. It is
known [7] that halogen atoms at the С=С bond are
hardly involved in the substitution or elimination
reactions. Contrary to the previous data [4, 5], when
studying the reactions of various dihaloalkanes with
MeSeLi and PhSeLi in THF the products of
substitution were obtained in good yields in all cases
[8]. cis-1,2-Dichloroethene under similar conditions
did not react with lithium methaneselenolate, although
substitution of chlorine by the MeSe group occurred
for this dichloride in ethanol when equimolar amount
of sodium ethylate was added. The authors of [8] did
not observe β-elimination neither for dichloro- nor
dibromoderivatives. The synthesis of unsaturated
selenacrown ethers was successfully performed by the
use of Na2Se (prepared in aqueous solution from
selenium, NaOH and rongalite) and cis-1,2-
dichloroethene in the presence of the phase transfer
catalyst [9]. No elimination of chlorine from
dichloroethene with the formation of acetylene was
detected.
As a rule, the reactions of nucleophilic substitution
of halogen by chalcogenide function result in the target
products in high yields and due to the softness of the
reacting nucleophile are rarely followed by elimination
of hydrogen halide. However, when using vicinal
dihalides, especially for the selenium and tellurium
derivatives, β-elimination of halogens and formation of
the corresponding olefin is possible [4, 5]. For the
sulfur-containing nucleophiles, only a few examples of
such elimination are known. Debromination of vicinal
dibromides under the action of Na2S.9H2O was
observed in the DMF solution for dibromides in which
both bromine atoms were attached to the sp3-
hybridized carbon atom as well as for 1,2-dibromo-
1,2-diphenylethene in which the bromine atoms are
Thus, the course of the reaction of chalcogene-
containing nucleophiles with vicinal dihalides is not
unequivocal and depends on the nature of halogen, the
structure of the dihalide (first of all on the character of
hybridization of the carbon atoms the halogens are
attached to) and on the nature of halogen in the
nucleophilic reagent.
1097

1098
LEVANOVA et al.
2,3-Dichloro-1-propene (I) may serve as an
increases to 2 : 1, the sulfide anions S2– are formed
rather selectively. The formation of potassium telluride
requires a large excess of alkali (KOH : Y = 8 : 1)
[10]. The solutions of K2S2, K2S and К2Те2 thus
obtained were introduced in the reaction with
dichloride I.
excellent model for investigation of the possibility of
substitution and elimination of halogens bound with
carbon atoms of different hybridization as a function of
the nature of the attacking chalcogenide anion. First of
all, we have studied the reactions of dihalide I with the
sulfur and tellurium anions since for these very anions
substantial differences in the course of the nucleophilic
reactions were observed [5].
Taking into account the possibility of the use of
disulfides in the synthesis of thiols and other organo-
sulfur compounds [11], we have first studied the
reaction of dichloride I with sulfur reduced by Eq. (1)
to the anions S22–. In the result of the reaction, bis(2-
chloro-1-propene-3-yl)sulfide (II) was obtained in
78% yield.
To transform sulfur and tellurium into the anionic
form Yn2– we have used the system hydrazine hydrate–
KOH [10]. Elemental sulfur and tellurium are reduced
in this system with the formation of potassium
polychalcogenides in which the value of n is
determined by the molar ratio KOH : chalcogene [10].
The data of elemental analysis and chromatomass
spectrometry prove that it is sulfide II (rather than the
anticipated disulfide) which is formed in reaction (2).
Such a course of the reaction may be due to instability
of disulfides having a halogen atom at the β-carbon
atom. The addition of sulfur monochloride to (S2Cl2)
to olefins is known to give, mainly, the corresponding
sulfides [12].
2nY + 4 KOH + N2H4·H2O → 2 K2Yn + N2 + 5 H2O, (1)
Y = S, Te.
At molar ratio KOH : Y = 1 : 1 the predominant
formation of dichalcogenide anions S22– and Te22– (n =
2) is observed; in the case of sulfur, when the ratio
K2S2
C CH2
Cl
C CH2Cl
CH2
S
CH2
2 CH2
C=CH2.
Cl
(2)
−2 KCl
−S
Cl
I
II
Apparently, by the same reason in the reaction of
1,2-dibromocyclohexane with sodium disulfide in the
system aqueous hydrazine–alkali bis(2-bromocyclo-
hexyl)sulfide (rather than disulfide) is formed [11].
0.8 Hz for hydrazine III and 4J = 0.9 Hz for sulfide II).
The signals of the olefinic protons in the cis-position to
the CH2N or CH2S group appear as doublets (2J =
1.5 Hz for hydrazine III and 2J = 1.4 Hz for sulfide II)
and those in the trans-position as doublets of triplets. It
is interesting to note that in hydrazine III the olefinic
proton in the trans-position resonates in a higher field
as compared to the cis-proton (by 0.03 ppm) whereas
in sulfide II vice versa, the trans-proton is deshielded
relative to the cis-proton by the same value. The
protons of the NH and NH2 groups give one wide
signal at 3.25 ppm.
Replacement of potassium disulfide by K2S in
reaction (2) (by using the ratio of KOH : S = 2 : 1
when dissolving sulfur in the system hydrazine
hydrate–alkali) does not accelerate the process. The
yield of sulfide II is even decreased (65%). In this
case, a side reaction of alkylation of hydrazine by the
starting dichloride I proceeds with the formation of (2-
chloro-1-propen-3-yl)hydrazine (III) in 13% yield.
The signals of both the Н (3.49 ppm) and 13С
1
C CH2
CH2
NHNH2.
I + N2H4
(3)
(60.68 ppm) of the CH2N group fall in the ranges
corresponding to the signals of the ОCH2 groups [13].
In order to unambiguously prove that these signals
correspond namely to the CH2 group attached to the
hydrazine fragment, that is, belong to compound III,
we have recorded the 2D HETCOR НМВС (1Н–15N)
spectrum with the Z-gradient pulse. The protons of the
−HCl
Cl
III
1H NMR spectrum of the obtained mixture of
compounds II and III contains the signals of hydrazine
III and sulfide II. The signals of the CH2N or CH2S
protons appear as doublets due to long-range coupling
with the olefinic proton in the trans-position (4J =
15
methylene group give a cross-peak with the N atom
of the NH2 group due to spin-spin coupling H2С–NH–
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REACTIONS OF 2,3-DICHLORO-1-PROPENE WITH SULFUR
1099
15NH2 through three bonds [δ(15N) = –316.8 ppm for
15NH2].
hydrate–KOH with 2,3-dichloro-1-propene (I) two
different processes are observed: nucleophilic
substitution of one chlorine atom in the 3 position in
the case of sulfur, and elimination of both chlorine
atoms in the case of tellurium. The course of the
reaction with tellurium is not affected even by the fact
that that one of the chlorine atoms is at the double
bond and must be inert with respect to nucleophilic
reagents. The reasons of different reactivity of the
sulfur- and telluriumcontaining nucleophiles are
determined both by different reductive ability of the
corresponding anions (for tellurium it is much higher),
and their size. It is evident, that an increase of the size
of the attacking nucleophile in the presence of rather
large adjacent group (in the present case, the chlorine
atom) leads to steric hindrances to classical
nucleophilic substitution.
With K2S2, hydrazine III is formed in reaction (2)
in 3–5% yield only when excess dichloride I is used.
It should be mentioned that in the synthesis of
chalcogenoorganic compounds in the hydrazine-
containing systems practically no alkylation of the
latter occurs [10]. It was shown by an independent
experiment that hydrazine III is the main product
(75% yield) in the reaction of 2,3-dichloro-1-propene I
with the system hydrazine hydrate–KOH. From this
reaction it can be isolated as an individual compound.
As evidenced by the results obtained, nucleophiles
S22– , S2– and hydrazine in the reactions with dichloride
I are capable of nucleophilic substitution of the
chlorine atom only at the sp3-hydridized carbon atom,
the chlorine atom at the double bond in these reactions
remains inert. Compounds II and III obtained in
reactions (2) and (3) are polyfunctional synthons and
can be used for preparation of practically valuable
substances.
EXPERIMENTAL
The reactions were monitored and the formed liquid
products analyzed by GC using an LKhM 80-MD-2
(column 2000×3 mm, liquid phase DC-550, 5% on
Chromaton N-AW-HMDS, linear temperature prog-
ramming 12 deg min–1, gas carrier helium). IR spectra
were recorded in thin layer on a Bruker IFS-25 Fourier
The reaction of potassium ditelluride (generated
from tellurium in the system hydrazine hydrate–alkali)
with dichloride I proceeds clearly and results in
elimination of both chlorine atoms with the formation
of allene IV (yield 78%) and recovery of elemental
tellurium (yield 98%).
1
spectrometer. H, 13C and 15N NMR spectra were
registered on a Bruker DPX 400 spectrometer
(working frequency 400.13, 100.62 and 40.55 MHz,
respectively) in CDCl3 solutions, internal standard for
1H, 13C are HMDS, for 15N is СН3NO2. Electron impact
(70 eV) mass spectra in the range 34–650 D were
K2Te2
C
CH2.
CH2
I
(4)
−2 KCl; −Te
IV
obtained
chromatomass
on
a
Shimadzu
GCMS-QP5050A
(column SPB-5,
spectro-meter
In this reaction we have first followed the relative
ability of chlorine atoms attached to carbon atoms of
different hybridization, to elimination. This is redox
reaction in which ditelluride anion acts as a reducing
agent and organic dichloride I as an oxidant.
60000×0.25 mm), stationary phase film thickness 0.25
μm; temperature of injector 200–250°С, gas carrier
helium, flow rate 0.7 ml min–1, temperature
programming from 60 to 200°С, 10 deg min–1,
temperature of detector 200°С, quadrupole mass
analyzer, temperature of ion source 190°С.
Reaction (4) may serve as a convenient synthetic
method for preparation of allene, which is used for
synthesis of a huge number of organic products [14].
Laboratory procedures for preparation of allene are
based on dehalogenation of 2,3-dichloro- or -dibromo-
1-propene with zinc metal, which during the course of
the reaction is completely converted into its chloride or
bromide and cannot be reused [15]. Quantitative
recovery of tellurium in reaction (4) allows its multiple
use for preparation of К2Те2 by Eq. (1) [16].
Bis(2-chloro-1-propene-3-yl)sulfide (II). a. To the
solution of 2.8 g of KOH in 20 g of hydrazine hydrate
at 80–85°С 1.6 g of powdered sulfur was added
portionwise. The mixture was kept at this temperature
during 2.5 h, cooled to room temperature, and 5.6 g of
2,3-dichloro-1-propene I was introduced dropwise and
stirred for 10 h at 45–50°С. The reaction mixture was
extracted with dichloromethane, ether, combined
extract dried with MgSO4. By the GC analysis, the
residue after removal of solvents was compound II of
~90% purity (4.99 g, yield 78%), bp 78–79 °С (4 mm Hg).
Therefore, in the reaction of anions generated from
elemental sulfur and tellurium in the system hydrazine
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 6 2009

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LEVANOVA et al.
IR spectrum, ν, cm–1: 3107, 2972, 2918, 1789, 1627,
cooled to –35°С, the calibrated second trap to –70°С)
and 2.78 g of dichloropropene I was added dropwise.
During the course of the reaction the precipitation of
tellurium was observed (6.3 g isolated) and the
reaction mixture turned from dark-crimson to
practically colorless. The formed allene IV was con-
densed in the second trap. The yield of allene IV was
determined from the volume of the liquid in the trap
(1.1 cm3, d4–70 0.7064 [14]). Its spectral characteristics
are given in our previous paper [16].
1408, 1382, 1209, 1113, 889, 841, 761, 683, 629, 521.
4
1H NMR spectrum, δ, ppm: 3.36 d (2H, CH2S, J = 0.9
2
Hz), 5.33 d, 5.36 d.t (2H, CH2=С, J = 1.4 Hz). 13C
NMR spectrum, δ, ppm: 38.62 (CH2S), 114.98 (CH2=),
137.78 (=CСl). Mass spectrum, m/z (for Cl-containing
ions, the peaks of 35Cl are given) (I, % to total ion
current): 147 (17.7) [M – Cl]+, 111 (3.0) [C3H5Cl2]+,
107, 106 (14.1) [C3H4SCl]+, [C3H3SCl]+×, 85 (2.5)
[C4H5S]+, 71 (11.1) [C3H3S]+, 61 (2.9) [C2H5S]+, 45
(29.0) [CHS]+, 39 (19.3) [C3H3]+. Found, %: C 39.49;
H 4.67; Cl 40.11; S 16.82. C6H8Cl2S. Calculated, %: C
39.34; H 4.37; Cl 39.34; S 17.49.
ACKNOWLEDGMENTS
This work was performed with financial support
from the Council of grants of the President of Russian
Federation for leading scientific schools (grant
no. NSh-263.2008.3) and Integration Program of SB
RAS “Chemical and materials sciences,” section 5.2
“Modern problems of chemistry of materials including
nanomaterials.”
b. To the sulfur solution prepared under the
conditions similar to those above in method a except
for 0.8 g of sulfur was added (molar ratio KOH : S =
2 : 1), 5.6 g of dichloride I was introduced, the mixture
was stirred for 12 h, cooled and extracted with CH2Cl2.
After solvent removal the mixture of sulfide II and
hydrazine III was obtained, which was analyzed by
1
GC, GC–MS and Н, 13С, 15N NMR spectroscopy
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