Reactions of 1,2-dihaloethanes with chalcogenide anions

Article abstract of DOI:10.1134/S1070428006050022

Reactions of 1,2-dihaloethanes with chalcogenide anions generated from elemental chalcogens and dimethylchalcogens were performed in the hydrazine hydrate-KOH system. The use of anions Se _x ^2- and Te _x ^2- (x = 1-4) resulted in ethylene evolution and chalcogen regeneration (or in increased x value in an anion). Oligomers of Thiokol type formed only in the reaction of the 1,2-dichloroethane with a mixture of potassium disulfide and diselenide. The reductive cleavage of oligomers obtained in the hydrazine hydrate-KOH system followed by methylation led to the formation of 1,2-bis(methylthio)ethane, 1-methylseleno-2- methylthioethane, and 1,2-bis(methylseleno)ethane. The features of substitution with chalcogenide anions in vicinal dihalides are discussed. Mass spectra of compounds obtained were measured and analyzed. Pleiades Publishing, Inc. 2006.

Full text of DOI:10.1134/S1070428006050022

ISSN 1070-4280 Russian Journal of Organic Chemistry, 2006, Vol. 42, No. 5, pp. 652-658. Ó Pleiades Publishing, Inc. 2006.
Original Russian Text Ó N.V. Russavskaya, V.A. Grabel’nykh, E.P. Levanova, E.N. Sukhomazova, L.V. Klyba, E.R. Zhanchipova, A.A. Tatarinova,
A.V. Elaev, E.N. Deryagina, N.A. Korchevin, B.A. Trofimov, 2006, published in Zhurnal Organicheskoi Khimii, 2006, Vol. 42, No. 5, pp. 672-678.
Dedicated to Academician of the Russian Academy of Sciences N.S. Zefirov
th
on occasion of his70 anniversary
Reactions of 1,2-Dihaloethanes with Chalcogenide Anions
N.V. Russavskaya, V.A. Grabel’nykh, E.P. Levanova, E.N. Sukhomazova, L.V. Klyba,
E.R. Zhanchipova,A.A. Tatarinova,A.V. Elaev, E.N. Deryagina, N.A. Korchevin, and B.A. Trofimov
Faworsky Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences, Irkutsk, 664033 Russia
e-mail: venk@irioch.irk.ru
Received July 8, 2005
Abstract—Reactions of 1,2-dihaloethanes with chalcogenide anions generated from elemental chalcogens and
2
-
2-
dimethylchalcogens were performed in the hydrazine hydrate–KOH system. The use of anions Se andTe (x =
x
x
1
–4) resulted in ethylene evolution and chalcogen regeneration (or in increased x value in an anion). Oligomers of
Thiokol type formed only in the reaction of the 1,2-dichloroethane with a mixture of potassium disulfide and
diselenide. The reductive cleavage of oligomers obtained in the hydrazine hydrate–KOH system followed by
methylation led to the formation of 1,2-bis(methylthio)ethane, 1-methylseleno-2-methylthioethane, and 1,2-
bis(methylseleno)ethane. The features of substitution with chalcogenide anions in vicinal dihalides are discussed.
Mass spectra of compounds obtained were measured and analyzed.
DOI: 10.1134/S1070428006050022
Polymers containing selenium and tellurium possess
valuable electrophysical characteristics [1–3], and
products of low molecular weight containing two or more
chalcogen atoms are efficient ligands in complex forma-
tion [4, 5] and promising for preparation of new bio-
logically active compounds [6]. We formerly developed
preparation methods for polymethyleneselenides, -di-
selenides, -sulfidoselenides, -ditellurides, -selenido-
tellurides, -sulfidoselenidotellurides based on the reactions
of chalcogens and their mixtures with dichloromethane
in a system hydrazine hydrate–KOH [7, 8].
not been reported, although both the chalcogen-containing
oligomers and the products which can be obtained thereof
(1,2-ethanediselenol or –ditellurol derivatives) may be of
interest from theoretical and practical viewpoint.
We carried out a systematical investigation of a re-
action between 1,2-dihaloethanes with elemental
chalcogens in a system hydrazine hydrate–KOH. In the
system were generated in situ potassium diselenides and
from the chalogens ditellurides [12, 13].
ꢀ
<ꢁꢀꢁꢀ.2+ꢁꢀꢁ1 + ꢁꢁ+ 2
Y=Se,Te.
ꢂ. < ꢁꢃꢁ1 ꢁꢃꢁꢄ+ 2
The reactions of 1,2-dihaloethane under similar condi-
tions are far less thoroughly studied. 1,2-Dichloroethane
readily reacted only with alkali metal polysulfides
furnishing in virtually quantitative yield oligomeric
polysulfides, Thiokols [9–11], widely used as sealants 9]
and for preparation of 1,2-ethanedithiol and its derivatives
It was found unexpectedly that reaction of 1,2-di-
haloethanes with K2Se2 and K2Òe2 resulted in ethylene
evolution and in the recovery of elemental halcogenes
in a free state. No oligomeric products were obtained.
Neither products of dehydrohalogenation of 1,2-dihalo-
ethanes (vinyl halides and acetylene) were detected.
[
10]. A similar reaction of 1,2-dibromoethane with
potassium polysulfide was also reported [11]. A reaction
of 1,2-dichloroethane with a solution of sulfur and
selenium in a system water–hydrazine hydrate–NaOH
yielded poly(ethylenesulfidoselenides) [7]. The main unit
in the macromolecules of these oligomers is assumed to
.
< ꢀꢀꢀ;&+ &+ ;
ꢁ<ꢀꢀ &+ &+
(1)
ꢁ
.;
X = Cl, Br.
Reaction (1) is formally a redox process where the
anionsY are reductants, and 1,2-dihaloethane is oxidant.
2
–
be –CH CH SSe– (or –SeCH CH S–). Selenium or
2
2
2
2
2
tellurium Thiokol analogs based on dihaloethanes have
Hence instead of a nucleophilic substitution reaction (1)
652

REACTIONS OF 1,2-DIHALOETHANES WITH CHALCOGENIDEANIONS
653
proceeds as 1,2-elimination of the halogen. At the same
time polyselenides were obtained from 1,3-dihalopropane
and Se in the system hydrazine hydrate–alkali and were
used for preparation of 1,3-propanediselenol derivatives
chalcogenide was treated with methyl iodide. The
treatment afforded elemental selenium (66%), dimethyl
diselenide (22%), and trace amounts of dimethyl selenide.
.
6H ꢁꢀꢁꢂ&+ ,
ꢅ[ꢁ!ꢁꢂꢆ
ꢅ&+ ꢆ 6H
[14].
ꢂ.,
ꢅ&+ ꢆ 6H ꢁꢀꢁ6H
The cause of this unexpected path of the reaction
ꢅ&+ ꢆ 6H
ꢂ
between 1,2-dihaloethanes and diselenide and ditelluride
anions may lie in the high reducing ability of the latter as
The instability of dialkylpolyselenides is well known
[17].
The reaction of 1,2-dichloroethane with an equimolar
2
–
compared to S2 anions enabling them to attack the
halogen atom to form a transition state (I).
;
2–
2–
mixture of dichalcogenide ions (S and Se ) was studied
2
2
in more detail (cf. [7]). In this case each anion was
generated separately from the elemental chalcogens in
an alkaline water solution of hydrazine hydrate [12, 18]
and they were mixed just before addition of the 1,2-di-
chloroethane. The resulting oligomeric product was of
nonuniform composition with inclusions of elemental
sulfur and selenium. The product was insoluble in organic
solvents, but completely dissolved in the system hydrazine
hydrate–KOH due to reductive cleavage of the bridges
S–S, Se–Se, and S–Se affording thiolates and selenolates
of low molecular weight [11, 14]. The subsequent alkyla-
tion of the latter with methyl iodide gave rise to the
corresponding methylthio and methylseleno derivatives.
The main two products of the reductive cleavage were
1,2-bis(methylthio)ethane (III) and 1-methylseleno-2-
methylthioethane (IV). No 1,2-bis(methylseleno)ethane
&
+
&+
< ;
ꢀ
&+ &+
(2)
ꢂ
;
,
<
;
,,
A similar mechanism was suggested for the reaction
of 2,3-dibromobutanes with sodium iodide affording
-butene [15]. Highly reactive dichalcogen halides II
2
arising in reaction (2) rapidly react with the other anions
2
–
Y .
2
,
,ꢁꢀꢁ<
<
ꢀꢁ;
2
–
Further involvement of anionsY in reaction (2) gives
rise to still longer polychalcogenide chains and finally
results in the formation of elemental chalcogens.
4
In reaction (1) (X = Cl) a potassium monoselenide
K Se) prepared in the system hydrazine hydrate–KOH
with no solvent added was also used [16].
(
V) was found among the reaction products. This
(
2
indicates that in the oligomer in question the –CH CH –
2
2
fragments of the molecule are bound either by disulfide
or by selenidosulfide bridges, and therefore the structure
of the oligomer and the scheme of its cleavage may be
described as follows.
ꢀ
6Hꢁꢀꢁꢂ.2+ꢁꢀꢁ1 + ꢁꢁ+ 2
ꢀ. 6Hꢁꢀꢁ1 ꢁꢀꢁꢃ+ 2
In further reaction of K Se with 1,2-dichloroethane
2
as in reaction (1) ethylene was evolved, no oligomer
products formed, but the elemental selenium did not
separated: The system remained homogeneous even at
the use of the triple excess of the 1,2-dichloroethane.
The conservation of the homogeneity of the system may
. 6 ꢀ
ꢀꢀ. 6H
ꢁ
ꢀ6&+ &+ 6ꢀꢀꢂꢀꢀꢁꢀ6&+ &+ 6Hꢀꢂ
&O&+ &+ &O
1
+ ꢀ+ 2ꢃ.2+
&
+ 6&+ &+ 6&+
2
–
be due to transformation of the Se anions into diselenide
.6&+ &+ 6.
ꢁꢁꢁꢁꢁꢁꢁꢁꢁꢀ
,
,,
&+ ,
2
–
2–
(
Se ) and polyselenide anions (Se ) well soluble in the
ꢀ
(4)
2
x
&
+ 6&+ &+ 6H&+
.
6&+ &+ 6H.
system hydrazine hydrate–KOH.
,
9
&+ &+ ꢁꢀꢁꢀ.&Oꢁꢀꢁ. 6H
The relative quantity of m and n units may be
approximately evaluated by the ratio of yields of com-
pounds III and IV equal to 2.5:1 (see EXPERIMENTAL).
The lack of bridges with two selenium atoms in the
macromolecule originates from the possibility of the
pathway through the transition state I and liberation of
the elemental selenium. The selenyl chloride (II) (X =
ꢀ
. 6Hꢁꢀꢁ&O&+ &+ &O
6Hꢁꢀꢁ. 6H ꢁꢀꢁ&O&+ &+ &O
ꢁ. 6H HWFꢂ
.
&+ &+ ꢁꢀꢁꢀ.&O
(3)
ꢀ
To prove the formation of anions Se2– (X ³ 2) by
x
reactions (3) the arising mixture of potassium poly-
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 42 No. 5 2006

654
RUSSAVSKAYA et al.
Cl) formed in this case by reaction (2) could also react
with polysulfide anions. Presumably this reaction results
in the formation of the elemental sulfur.
6
H&+ &+ &Oꢀꢀꢀ6H ꢀꢁꢀꢀ&O&+ &+ 6
6H&+ &+ 6H &+ &+ 6
ꢁ
&O
selenide anion of the already existing macromolecules
with the terminal chlorine atoms [contrary to reaction
6H &Oꢀꢀꢀ6
ꢁ6H 6 ꢂ
&O
(
2)].
The completion of reaction (4) revealed by the total
decoloration of the polychalcogenide solution required
twice as much 1,2-dichloroethane as corresponded to the
stoichiometric amount according to the reaction equation.
This fact may be caused by the repeated activation of
elemental selenium (or sulfur) with hydrazine [19] for
the hydrazine hydrate is used in excess.
The yield of bisselenide V indicates that the probability
of such fragments formation is very low.
The structure of compounds III and IV is confirmed
1
by H NMR method (see EXPERIMENTAL), and that
of all three compounds III–V was proved by GC-MS
procedure. Compounds III–V at electron impact furnish
sufficiently stable molecular ions that appear in the mass
spectra as peak clusters characteristic of the presence
in the molecule of two sulfur atoms in compound III, one
in compound IV, and of two selenium atoms in compound
V. Mass spectrum of compound IV was measured for
the first time, those of compounds III and V were already
published [20–22] and registered in the standard electronic
library NIST. This fact helped in confirming structures
III and V.
ꢀ6Hꢁꢀꢁꢂ1 + ꢁ+ 2
ꢃꢄ1 + ꢅ 6H ꢁꢀꢁ1 ꢁꢀꢁꢂ+ 2
At the higher ratio Se:S in reaction (4) (2:1 and 4:1)
the yield of the oligomers formed increased, and the
selenium content also grew, but apparently only owing to
the larger amount of the elemental selenium. The reductive
cleavage of these oligomers resulted in the same com-
pounds III and IV whose overall yield attained 35 and
1
8% respectively, and their ratio insignificantly changed
The characteristic ions and the probable paths of their
formation for compound IV are given on the scheme.
The intensity is reported as percent to the total ionic
current. The main fragmentation processes as in the case
in favor of compound IV. However in these reaction
products 1,2-bis(methylseleno)ethane (V) was detected,
0.5% at the ratio Se:S = 2:1, and around 1% at the ratio
4
:1 (according to GLC and GC-MS data). The structure of compounds III and V are initiated both by the radical
of oligomers obtained at these ratios and the character
of products arising at their reductive cleavage followed
by methylation may be described as follows.
center and by the charged species, and they consist in
a simple rupture of the C–C bonds. The first pathway
provides the corresponding radicals, the second even ions.
The peaks of S-containing ions are as a rule stronger
ꢅꢁ6&+ &+ 6ꢁꢆ
ꢊꢁE
ꢅꢁ6&+ &+ 6Hꢆ ꢁꢁꢁꢁꢅ6H&+ &+ 6Hꢆ
+
than the Se-containing. The most abundant ion is [C H S]
N
3 7
of m/z 75 (29.9). Besides in the spectrum appear peaks
ꢊꢁE
ꢊꢁE
+
80
+
of rearranged ions [CHSe] of m/z 93 (6.0),( Se), [CHS]
+
&
+ 6H&+ &+ 6H&+
9
B
of m/z 45 (3.6), and [C H ] of m/z 41 (16.4).
3
5
,,,
,9
Analysis of the fragmentation of the molecular ion of
compound IV revealed that the probability of rupture is
significantly higher for C–Se bond than for C–S bond.
B
1
+ ꢁ+ 2ꢇ.2+ꢈꢁEꢁꢁꢁꢁ&+ ,ꢉ
8
0
The formation of bisselenide fragments in these
oligomers apparently occurred by coupling with a di-
Ions of m/z 75 and 123 ( Se isotope), respectively, are
diagnostic for detecting the fragments CH YCH CH –:
3
2
2
Scheme.
+ 6HꢁꢁꢁPꢀ]ꢁꢋꢄꢁꢅꢂꢌꢉꢌꢆ
&
&
+ 6HꢁꢁꢁPꢀ]ꢁꢍꢎꢁꢅꢄꢉꢋꢆ
&
+ 6HꢁꢁꢁPꢀ]ꢁꢀꢋꢁꢅꢎꢎꢉꢄꢆ
6
+ & &+ &+ 6H&+
Pꢀ]ꢁꢌꢄꢁꢅꢍꢉꢀꢆꢁꢀꢁ& + 6
Pꢀ]ꢁꢎꢏꢌꢁꢅꢀꢉꢄꢆꢁꢀꢁ& + 6
Pꢀ]ꢁꢎꢂꢐꢁꢅꢀꢉꢄꢆꢁꢀꢁ&+ 6
,
9ꢊꢁ0 ꢎꢋꢏꢁꢅꢎꢎꢉꢄꢆ
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 42 No. 5 2006

REACTIONS OF 1,2-DIHALOETHANES WITH CHALCOGENIDEANIONS
655
;
For Y = S the ion with m/z 75 is present in the spectrum,
for Y = Se that of m/z 123. The presence of these ion
peaks we used for identification of minor products heavier
than compounds III and V which were formed at the
cleavage of the oligomers.
&
+ 6H
&+
&+
>&+ 6H;@
ꢃ&+ ꢄ 6H
6)
;
;
;
;
6H&+
(
Compound VI: CH SCH CH SCH CH SeCH (yield
The generation of a small quantity of compound V is
3
2
2
2
2
3
.
0
.3%) M + 230, diagnostic ions of m/z 75 and 123 are
probably due to a successive attack on the carbon atoms
–
present.
of the substrate of two CH Se anions, since the already
3
formed CH Se–CH bond is stable under the conditions
Compound VII: CH SeCH CH SCH CH SeCH
yield 0.3%) M 278, strong peak of ion with m/z 123,
ion of m/z 75 is lacking.
3
2
3
2
2
2
2
3
+
.
of reaction (5), for compound V (same as compound IV)
does not change in the system hydrazine hydrate–KOH.
Apparently the similar situation was observed when
compound V was synthesized from selenium, methyl-
lithium, and 1,2-dichloroethane in ethyl ether solution (yield
of compound V 53%) [22].
(
Compound VIII: CH SCH CH SeCH CH SeCH
3
2
2
2
2
3
+
.
(
yield 1%) M 278, ions of m/z 75 and 123 are present.
Compound IX: CH SeCH CH SeCH CH SeCH
yield 1%) M + is lacking, strong peak of ion with m/z
3
2
2
2
2
3
.
(
1
23, 95 (CH Se), ion of m/z 75 is lacking.
3
ꢁꢂ&+ 6Hꢃ ꢀꢀꢀꢄ1 + ꢀ+ 2
ꢅ1 + 6H&+ ꢀꢀꢀ1 ꢀꢀꢀꢄ+ 2
The formation of compounds VI–IX indicates the
The dimethyl diselenide arising by reaction (6) is
presence in the solution of the initial potassium dichalco-
2–
2–
constantly activated with excess hydrazine hydrate used
genides of monochalcogenide anions (S and Se ) which
afford monochalcogenide units in the oligomer chain.
–
as solvent affording anions CH Se [25].
3
In the reaction of an equimolar mixture of Na S and
The presence of elemental selenium in the oligomers
was confirmed by the formation of dimethyl selenide and
dimethyl diselenide in the course of reductive cleavage
of the oligomers followed by methylation; the preparation
of these compounds from the elemental selenium had
been described in [12].
2 2
Na Te (separately generated [13, 16]) with 1,2-dichloro-
2
2
ethane no oligomer products were obtained. Alongside
ethylene we obtained a black powder of a mixture of
elemental sulfur and tellurium. This was confirmed by
the reaction of the powder with the system hydrazine
hydrate–KOH giving rise to a deeply colored solution.
The subsequent methylation of the solution yielded
a mixture of Me S and Me Te. In this mixture even
Compound III we previously synthesized from dimethyl
disulfide and dichloroethane in a sytem hydrazine hydrate–
alkali metal hydroxide in an 82–85% yield [23].
2
2
compound III was lacking according to GLC and
GC-MS.
We attempted to prepare compound V by a similar
procedure.
1
+ ꢁꢁ+ 2ꢇ.2+
ꢅ&+ ꢆ 7H
ꢂ&+ 7H.
ꢀ
ꢁ&+ ꢂ 6H ꢃꢀꢃ1 + ꢃ+ 2ꢃꢀꢃꢄ.2+
&
O&+ &+ &O
ꢂ.&O
ꢄ&+ 6H.ꢃꢀꢃ1 ꢃꢀꢃꢅ+ 2
&+
&+ ꢁꢀꢁꢅ&+ ꢆ 7H
9
ꢀ
&+ &+ ;
.;
The attempt to prepare bis(methyltelluro)ethane from
dimethyl ditelluride and 1,2-dichloroethane in the system
hydrazine hydrate–KOH [see reaction (5)] resulted in
ethylene formation and complete recovery of dimethyl
ditelluride. The presence of a small amount of dimethyl
telluride was due to the partial decomposition of the
dimethyl ditelluride [17].
;
&
+ 6H.
(5)
ꢁ
&+ ꢂ 6H ꢃꢀ &+ &+
ꢀ
.;
Dimethyl diselenide in the system hydrazine hydrate–
KOH was completely reduced and afforded a homo-
geneous solution [24]; however the treatment of the
solution obtained with the double excess of 1,2-dibromo-
or 1,2-dichloroethane with respect to the stoichiometric
amounts according to reaction (5) gave rise to ethylene,
compound V (20%), and half of the dimethyl diselenide
Hence the reaction of 1,2-dihaloethanes with
chalcogenide anions takes two probable routes:
nucleophilic substitution and dehalogenation involving
ethylene evolution and oxidative coupling of the
chalcogenide anions. With selenium and especially with
tellurium the second route is prevailing.
(
53%) was recovered.Apparently here reaction occurred
analogous to reaction (2) through a transition state X.
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 42 No. 5 2006

656
RUSSAVSKAYA et al.
EXPERIMENTAL
IR spectra of products were measured on spectro-
confirmed the presence of ethylene. The negative test
with Ilosvay reagent indicated the absence of acetylene
in the gas obtained. On completion of 1,2-dichloroethane
addition the mixture was heated to 70–75°C for 7 h, cooled
to 20–25°C, and within 0.5 h into the reaction mixture
photometers Specord-75IR (from thin films) and Bruker
1
IFS-25 (from pellets with KBr). H NMR spectra were
registered on spectrometer Bruker DPX-400 (400.1 MHz)
1
4.2 g (0.1 mol) of methyl iodide was introduced. The
from solution in CDCl , internal reference HMDS.
3
reaction proceeded with heat evolution, separation of
elemental selenium (1.8 g), and formation of a viscous
black tarry product (2 g). The latter two substances were
separated from the water layer and extracted with ethyl
ether. On removing the solvent from the extract we isolated
virtually pure dimethyl diselenide (GLC, comparison with
reference), yield 1.2 g (22% calculated on selenium used
in the reaction). Additional 0.8 g of elemental selenium
was isolated from the tarry product, overall yield of Se
Mass spectra were obtained on an instrument
ÒM
SHIMADZU CMS-QP5050A, column SPB -5, 60 m
long, internal diameter 0.25 mm, stationary phase film
0
.25 mm thick; injector temperature 250°C, carrier gas
-1
helium, flow rate 0.7 ml min , oven temperature program
-
1
from 60°C, ramp 15°C min to 260°C, detector tempera-
ture 250°C. Quadrupol mass-analyzer, electron impact
ionization, electrons energy 70 eV, ion source temperature
2
00°C, detected mass range 34–650 D.
2
.6 g (66%).
The liquid products obtained were analyzed on
Reaction of 1,2-dichloroethane with selenium
tellurium) in a system hydrazine hydrate–water–
a chromatograph LKhM 80-MD-2, column 2000´3 mm,
(
-
1
liquid phase XE-60 (5%), ramp ramp 12°C min , carrier
KOH. To a solution of 2.8 g (0.05 mol) of KOH in 15 ml
of water containing 2.5 g (0.05 mol) of hydrazine hydrate
was added at 60–80°C 3.95 g (0.05 mol) of selenium
powder. The mixture was maintained for 2 h at 80–
85°C [12], cooled to 45°C, then to the solution of K Se
gas helium.
Gas analysis was carried out on a chromatograph
Tsvet-100 eqiupped with a flame ionization detector,
column 3000 ´ 3 mm, oven temperature 80°C, solid phase
modified alumina.
2
2
thus obtained was introduced 9.9 g (0.1 mol) of 1,2-di-
chloroethane. The reaction occurred with heat evolution
and ethylene liberation (1,2-dibromoethane formation in
the solution of Br2 in CCl4) and with separation of
elemental selenium which was filtered off, washed in
succession with water and acetone, and dried. Yield
3.6 g (91%).
Reaction of 1,2-dichloroethane with selenium in
a system hydrazine hydrate–KOH. To a solution of
7
g (0.125 mol) of KOH in 25 g (0.5 mol) of hydrazine
hydrate at 60–80°C was added by portions within 1 h
.95 g (0.05 mol) of selenium powder. The reaction
mixture was maintained for 2 h at 80–85°C [16], cooled
to 45°C, and at this temperature to the obtained solution
3
In a similar reaction of 4.95 g (0.05 mol) of 1,2-di-
chloroethane with potassium ditelluride prepared from
.38 g (0.05 mol) of tellurium powder, 5.6 g (0.1 mol) of
KOH, and 25 g (0.5 mol) of hydrazine hydrate was proved
ethylene formation (as above) and was isolated 6.0 g
94%) of metallic tellurium.
of K Se was added dropwise 2.47 g (0.025 mol) of
2
1
,2-dichloroethane. The reaction occurred with heat
6
evolution and gas liberation. The gaseous products were
passed through traps cooled to –40°C and then bubbled
through a solution of bromine (4 g) in carbon tetrachloride
(
(
30 ml). On adding the calculated quantity of 1,2-di-
Reactions of 1,2-dibromoethane with solutions of
selenium and tellurium were carried out in the same
fashion.
chloroethane the reaction mixture remained homogeneous
2
–
and deeply colored indicating the presence Se anions.
x
Therefore two portions of dichloroethane, 0.025 mol
each, were added dropwise in succession to the reactor.
Reaction of 1,2-dichloroethane with an equimolar
mixture of potassium disulfide and diselenide.
A solution of potassium disulfide was prepared from
5.6 g (0.1 mol) of KOH, 5 g (0.1 mol) of hydrazine hydrate,
30 ml of water, and 3.2 g (0.1 mol) of sulfur powder at
65–70°C. Under similar conditions in another flask
potassium diselenide solution was prepared from 7.9 g
(0.1 mol) of selenium powder. Into the combiner solution
29 g (0.4 mol) of 1,2-dichloroethane was added. The
formed oligomer was separated, washed with water, with
The complete decoloration of the solution of 4 g of Br in
2
CCl was attained after adding dropwise into the reaction
4
mixture of 3.1 g (0.031 mol) of 1,2-dichloroethane, and
therewith ethylene was obtained in an 80% yield. The
absorption of the gas products by the bromine solution
afforded the only compound, 1,2-dibromoethane (GLC
and GC-MS data). No products of vinyl chloride or
acetylene bromination were found in the CCl solution.
4
The GC analysis of the gas flushed with argon flow
RUSSIAN JOURNALOF ORGANIC CHEMISTRY Vol. 42 No. 5 2006

REACTIONS OF 1,2-DIHALOETHANES WITH CHALCOGENIDEANIONS
657
acetone, and dried. The oligomer was ground into powder
and extracted with boiling benzene to isolate 0.6 g (19%)
of elemental sulfur. The residue (10.1 g) was a powder
of dark claret color, mp 85–150°C (decomp.). IR
introduced into a solution of 11.2 g (0.2 mol) of KOH in
20 g (0.4 mol) of hydrazine hydrate. On complete
dissolution of the powder the solvent was heated for 2 h
at 85–90°C, cooled to 20–25°C, and at this temperature
15.4 g (0.108 mol) of methyl iodide was added dropwise.
The formed organic layer was separated, washed with
–
1
spectrum, n, cm : 2915, 1406, 1233, 1187, 1163, 1089,
1
6
026, 784, 762, 718, 675, 602, 496, 475. Found, %: C
.30; H 1.35; Cl 2.43; S 25.30; Se 77.18. In a similar
water, and dried with MgSO . We obtained 3.65 g of
4
way at the ratio S:Se = 1:2 (1.6 g of sulfur and 7.8 g of
selenium) we obtained 7.6 g of oligomer with notable
inclusions of elemental selenium, t.decomp. 80–185°C.
Found, %: S 14.06; Se 86.83. At the ratio S:Se = 1:4
a mixture, consisting of 0.75 g (42%) of dimethyl sulfide
and 2.90 g (74%) of dimethyl telluride, which were
identified by GLC by comparison with authentic samples.
Bis(methylseleno)ethane (V). At 30°C 2.3 g
(
0.8 g of sulfur and 7.8 g of selenium) we obtained 8.0 g
(0.012 mol) of dimethyl diselenide was added to a solution
of nonuniform product with the selenium content 88.14%,
t.decomp. 65–190°C.
of 3.4 g (0.06 mol) of KOH in 15 g (0.3 mol) of hydrazine
hydrate. The mixture was stirred for 1.5 h at 75–80°C.
On cooling to 20°C 4.58 g (0.24 mol) of 1,2-dibromo-
ethane was added at stirring. The reaction with heat
evolution and ethylene liberation (see above) did not result
in changing the dark claret color of the solution. The
mixture was diluted with water (50 ml) and extracted
Bis(methylthio)ethane (III) and 1-methylseleno-
2
-methylthioethane (IV). To a solution of 8 g
(0.14 mol) of KOH in 35 g (0.7 mol) of hydrazine hydrate
was added by portions at 50°C 3.8 g of oligomer prepared
by reaction (4). The reaction mixture was stirred for 2 h
at 70–75°C, cooled, and at 20–25°C into the homogeneous
solution 15.4 g (0.108 mol) of methyl iodide was added.
The mixture was stirred for 0.5 h at 40–42°C and then
cooled. The reaction products were extracted into
CH Cl , the extract was dried with MgSO . The solvent
with ether. The extract was dried with MgSO . On
4
distilling off ether we obtained a residue (2.42 g) that
according to GLC and GC-MS contained 18% of
1,2-bis-(methylseleno)ethane (V) (yield 20% with respect
to the taken dimethyl diselenide) and 76% of dimethyl
2
2
4
1
was distilled off, the residue was kept for 0.5 h at the
pressure of 5 mm Hg, and thus a mixture of compounds
was obtained: 1.06 g (59% with respect to S content in
diselenide (recovered in a 53% ). H NMR spectrum of
compound V, d, ppm: 2.05 s (CH Se), 2.83 s (CH Se).
3
2
8
0
+
Mass spectrum (m/z value is given for Se): 218 [M ],
123 [M – SeCH ] , 95 [SeCH ] . The spectral character-
1
+
+
the oligomer) of bis(methylthio)ethane (III) [ H NMR
3 3
spectrum, d, ppm: 2.13 s (CH S), 2.75 s (CH S)], and
istics are consistent with the published data [22].
3
2
1
.41 g (23% with respect to Se content in the oligomer)
Reaction of dimethyl ditelluride with 1,2-di-
chloroethane. To a solution of 5.04 g (0.09 mol) of KOH
in 22.5 g (0.45 mol) of hydrazine hydrate was added at
35–40°C 4.9 g (0.017 mol) of dimethyl ditelluride. The
reaction mixture was stirred for 2 h at 80–85°C, cooled,
and at 25–30°C into the homogeneous solution was added
3.36 g (0.034 mol) of 1,2-dichloroethane. The reaction
was performed and workup was carried out as described
above for the dimethyl diselenide. The solution was
extracted with CH Cl . According to the data of GLC,
1
of 1-methylseleno-2-methylthioethane (IV) [ H NMR
spectrum, d, ppm: 1.25 s (CH Se), 2.03 s (CH S),
2
3
3
.78 m (CH S, CH Se)].
2 2
Reaction of 1,2-dichloroethane with an equi-
molar mixture of potassium disulfide and ditellu-
ride. A solution of potassium disulfide solution was
prepared from 2.8 g (0.05 mol) of KOH, 2.5 g (0.05 mol)
of hydrazine hydrate, 15 ml of water, and 1.6 g
(
0.05 mol) of sulfur powder as described above. The
2
2
1
solution of K Òe was prepared from 6.38 g (0.05 mol)
GC-MS, and H NMR the extract contained 30% of
dimethyl telluride and 70% of dimethyl ditelluride.
2
2
of tellurium powder, 5.6 g (0.1 mol) of KOH, and 25 g
0.05 mol) of hydrazine hydrate. The solutions were
(
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