Reactions of 1,1-Dichloroethene with elemental chalcogens in the system hydrazine hydrate–alkali

Full text of DOI:10.1134/S1070428016070307

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2016, Vol. 52, No. 7, pp. 1070–1071. © 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. 7, pp. 1075–1076.
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COMMUNICATIONS
Reactions of 1,1-Dichloroethene with Elemental Chalcogens
in the System Hydrazine Hydrate–Alkali
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 April 22, 2016
DOI: 10.1134/S1070428016070307
1,1-Dichloroethene (1, vinylidene chloride) is
an important monomer for the manufacture of
chlorine-containing polymers and copolymers [1].
Nucleophilic substitution of the chlorine atoms linked
to sp2-carbon atom of vinylidene chloride is generally
difficult to accomplish; therefore, there are almost no
published data on the synthesis of organochalcogen
compounds from vinylidene chloride and even from
its derivatives. Nevertheless, transformations of 1 into
unsaturated chalcogenides may be quite promising
from the viewpoint of the design of novel reagents for
organochalcogen synthesis, monomers, ligands for
complexation with metals, and biologically active
compounds.
with sulfur (as K2S) we isolated 1,4-dithiine (2) as the
only product (yield 27%, unoptimized; Scheme 2).
Scheme 2.
S
Cl
S8–KOH–N2H4·H2O
H2C
Cl
S
1
2
Compound 2 is a fairly rare sulfur-containing
heterocycle with two sulfur atoms. Sun and Yang [3]
previously reported the reaction of 1 with sodium
sulfide nonahydrate in acetonitrile in the presence of
15-crown-5, which afforded a mixture of 2 (~15%) and
macrocyclic thiacrown ethers (39%). 1,4-Dithiine (2)
was also obtained in 68% yield from difficultly
accessible diethynyl sulfide and Na2S (prepared from
sulfur and sodium metal in liquid ammonia) [4] and
in 82% yield from 1,4-dithiane-2,5-diol and thionyl
chloride in anhydrous DMF [5]. The procedure for the
synthesis of 2 proposed by us is advantageous due to
high selectivity, accessibility of the initial compounds,
and experimental simplicity.
Elemental selenium and tellurium, as well as sulfur
(in most cases), are fairly inert toward many organic
compounds. On the other hand, these elements become
efficient nucleophiles after preliminary redox activa-
tion to the Yn2– state (Y = S, Se, Te; n = 1–4) [2].
Elemental chalcogens are readily activated with the
system hydrazine hydrate–alkali [2] (Scheme 1).
Scheme 1.
In the reactions of 1 with selenium and tellurium
we isolated diethyl selenide (3a, 29%) and diethyl
telluride (3b, 22%; Scheme 3). The yields of 2 and 3
were calculated with respect to the initial chalcogen.
2Y + N2H4·H2O + 4KOH
2K2Y + N2 + 5H2O
Selective formation of monochalcogenide ions
(Y2–) requires excess alkali (Y–KOH ratio 1:2.5 to
1 :8). The resulting chalcogenides can be used in
further syntheses without isolation.
Scheme 3.
Y–KOH–N2H4·H2O
Vinylidene chloride reacts with all these chalcogens
in the system hydrazine hydrate–KOH under fairly
mild conditions (25°C, 3 h), but the products of these
reactions were essentially different. In the reaction of 1
1
Et2Y
3a, 3b
Y = Se, Te.
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REACTIONS OF 1,1-DICHLOROETHENE WITH ELEMENTAL CHALCOGENS
1071
Thus, sulfide ion reacts with 1 via nucleophilic sub-
stitution of the chlorine atoms, whereas the reactions
of 1 with selenium and tellurium are accompanied by
profound reduction. Reductive substitution of a halo-
gen atom by hydrogen by the action of tellurium
nucleophiles has been reported fairly frequently [6];
however, only hydrogenation of double bond in the
system hydrazine hydrate–alkali [7] and reduction of
activated benzyl halides with RSe– ions (R = Me, Et,
Ph) [8] is known for selenium nucleophiles.
(77Se), or Me2Te (125Te) as internal standard. The mass
spectra (electron impact, 70 eV) were obtained on
a Shimadzu GCMS-QP5050A instrument (SPB-5
column, 60000×0.25 mm; quadrupole mass analyzer,
ion source temperature 190°C, a.m.u. range 34–650).
The main results were obtained using the facilities
of the Baikal Joint Analytical Center, Siberian Branch,
Russian Academy of Sciences.
REFERENCES
Reductive activation of chalcogens with the system
hydrazine hydrate–KOH was achieved according to the
procedure described in [2], the Y/KOH ratios being
1:4, 1:5, and 1:8 for sulfur, selenium, and tellurium,
respectively. Excess vinylidene chloride (Y/1 1:3) was
then added to the resulting chalcogenide-containing
solution at 25°C, and the product was isolated by
extraction with Et2O. Removal of the solvent from the
extract gave almost pure compound 2, 3a, or 3b.
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1,4-Dithiine (2). Red liquid, bp 78°C (20.5 mm);
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1
published data [9]: bp 77–79°C (15 mm). H NMR
spectrum: δ 6.19 ppm, s. 13C NMR spectrum:
δC 121.20 ppm (cf. [3–5]). Mass spectrum: m/z 116
[M]+. Found, %: C 41.17; H 3.50; S 54.72. C4H4S2.
Calculated, %: C 41.35; H 3.47; S 55.18.
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Diethyl selenide (3a) and diethyl telluride (3b)
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and Grabel’nykh, V.A., Russ. Chem. Bull., 1998, vol. 47,
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1
The N, 13C, 77Se, and 125Te NMR spectra were
8. Hevesi, L., Tetrahedron Lett., 1979, vol. 20, no. 32,
recorded on a Bruker DPX-400 spectrometer at
400.13, 100.62, 76.31, and 126.2 MHz, respectively,
using CDCl3 as solvent and TMS (1H, 13C), Me2Se
p. 3025.
9. Parham, W.E., Gadssy, B., and Mikulec, R.A., J. Org.
Chem., 1959, vol. 24, p. 1819.
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