Stereoselective synthesis of (E,E)-bis(2-halovinyl) selenides and its derivatives based on selenium halides and acetylene

Article abstract of DOI:10.1016/j.tet.2012.09.099

Efficient stereoselective synthesis of (E,E)-bis(2-chlorovinyl) and (E,E)-bis(2-bromovinyl) selenides in 95-98% yield based on the reactions of selenium dihalides or monohalides with acetylene has been elaborated. Reactions of selenium tetrahalides with a

Full text of DOI:10.1016/j.tet.2012.09.099

Tetrahedron 68 (2012) 10567e10572
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Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Stereoselective synthesis of (E,E)-bis(2-halovinyl) selenides and its derivatives
based on selenium halides and acetylene
Maxim V. Musalov, Vladimir A. Potapov , Maria V. Musalova, Svetlana V. Amosova *
*
A. E. Favorsky Irkutsk Institute of Chemistry, Siberian Branch of the Russian Academy of Sciences, 1 Favorsky Str., RUS-664033 Irkutsk, Russia
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 10 July 2012
Received in revised form 24 September
Efficient stereoselective synthesis of (E,E)-bis(2-chlorovinyl) and (E,E)-bis(2-bromovinyl) selenides in
9
5e98% yield based on the reactions of selenium dihalides or monohalides with acetylene has been
elaborated. Reactions of selenium tetrahalides with acetylene afford (E,E)-bis(2-halovinyl) selenides and
E)-2-halovinyl 1,2,2-trihaloethyl selenides. Convenient synthesis of (E,E)-bis(2-halovinyl) selenium
2012
(
Accepted 25 September 2012
Available online 29 September 2012
dihalides in near quantitative yield has been developed. (E,E)-Bis(2-halovinyl) selenium dihalides
undergo spontaneous rearrangement with the halogen migration from the selenium atom to the double
bond. The previously described reactions of selenium monochloride and tetrabromide with acetylene
have been reinvestigated.
Keywords:
Acetylene
Selenium dihalides
Selenium monohalides
Selenium tetrahalides
Ó 2012 Elsevier Ltd. All rights reserved.
1. Introduction
disproportionation to Se
mide converted to Se Br
2
Cl
2 4
and SeCl , whereas selenium dibro-
12
2
2
and bromine. Nevertheless, we found
Selenium was considered a poison for many years, until
Schwarz and Foltz identified it as an essential micronutrient for
human beings.1 Since then, there has been growing interest to
organoselenium chemistry and compounds with various types of
that freshly prepared selenium dichloride and dibromide can be
used in situ for selective synthesis of organoselenium compounds
7e11
including heterocycles.
The reaction of selenium dichloride and
dibromide with dimethyl diethynyl silane leading to selenasila-
2
biological activity have been found. Vinylic selenides play a special
fulvene derivatives represented the first synthesis of an organo-
7
role in organoselenium chemistry serving as versatile precursors and
selenium compound using selenium dihalides.
3
synthons in organic synthesis. The most general approach to vinylic
Recently we studied the reactions of selenium dichloride and
8
9
selenides is the nucleophilic addition of selenium nucleophiles to
dibromide with divinyl sulfide, divinyl selenide and divinyl sul-
4
10
alkynes. The addition of selenium electrophiles to alkynes may be
fone leading to novel four-, five- and six-membered selenium
heterocycles. Efficient methods for preparation of divinyl sulfide
and divinyl selenide were earlier elaborated based on addition of
1
a,13
regarded as another efficient synthetic approach to vinylic selenides
5
14
on condition that these reactions are regio- and stereoselective.
Selenium tetrahalides are commonly used electrophilic reagents
for organoselenium chemistry. However, reactions of these re-
sulfide and selenide anions to acetylene.
5
agents often lead to mixtures of products, e.g., diorganylselenium
2
. Results and discussion
5
,6
dihalides, diorganyl selenides and halogenated compounds. It has
7e11
been demonstrated that selenium dichloride and dibromide,
The reactions with acetylene are important from both practical
are more selective and efficient electrophilic reagents for prepara-
tion of diorganyl selenides compared with selenium tetrahalides.
Although the presence of selenium dichloride and dibromide in the
gas phase and in solutions has been demonstrated in the literature,
none of the selenium dihalides was isolated as a pure compound.12
It has been shown that in solution, selenium dichloride underwent
and theoretical viewpoints. In this work, we report a full account
of our studies on reactions of selenium dihalides, tetrahalides
and monohalides with acetylene including reinvestigations of
previously described reactions of selenium monochloride and tet-
rabromide with acetylene. Preliminary results of these studies were
15
published as short communications without experimental details.
Selenium dichloride was prepared from selenium and sulfuryl
chloride in carbon tetrachloride, chloroform or methylene chloride,
while selenium dibromide was obtained from selenium and
bromine in the same solvents.
*
Corresponding authors. E-mail addresses: v.a.potapov@mail.ru (V.A. Potapov),
amosova@irioch.irk.ru (S.V. Amosova).
0
040-4020/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tet.2012.09.099

10568
M.V. Musalov et al. / Tetrahedron 68 (2012) 10567e10572
1
6
Several examples of reactions of acetylene with selenium
are absent in the Ref. 16a; authors presented only analytical data
(the contents of selenium and chlorine).
monochloride,1 tetrachloride
6a
16b
and tetrabromide
16c,d
were pre-
viously described in the literature. The addition of selenium tetra-
Taking into account high reactivity of organylselenenyl chlo-
rides, we questioned the formation of (E)-2-chlorovinylselenenyl
chloride as the product in the reaction of selenium monochloride
ꢁ
chloride to acetylene (diethyl ether at ꢀ78 C) afforded
16b
bis(2-chlorovinyl)selenium dichloride in 9% yield.
The spectral
16a
characteristics and stereochemistry of this product were not pre-
sented. Bis(2-bromovinyl)selenium dibromide was obtained from
acetylene and selenium tetrabromide, which was generated from
with acetylene, although this compound can be an intermediate
in this reaction. We studied the reaction of selenium monochloride
with acetylene under the conditions, which were indicated in the
16c
ꢁ
selenium dioxide and hydrobromic acid. However, the yield and
stereochemistry of the product were not reported.
Ref. 16a (benzene, 2e4 C). We found that the reaction led to sel-
enide 1 (30% yield) rather than to (E)-2-chlorovinylselenenyl
chloride (Scheme 2). The best yield (95%) of selenide 1 was
reached when the reaction was carried out under the pressure of
We studied the reactions of selenium dichloride and dibromide
with acetylene under the pressure in an autoclave as well as under
ambient conditions. The reaction afforded (E,E)-bis(2-chlorovinyl)
selenide (1) and (E,E)-bis(2-bromovinyl) selenide (2) in many sol-
ꢁ
acetylene in an autoclave (10e12 atm, 30e40 C) using carbon
tetrachloride as a solvent. The process was concomitant with the
precipitation of elemental selenium.
4
vents, such as CCl , chloroform, methylene chloride, acetonitrile and
diethyl ether. However, carbon tetrachloride was the best among
studied solvents in respect to chemo- and stereoselectivity. In this
solvent, the reaction proceeded in chemo- and stereoselective
manner to afford selenides 1 and 2 as the only products (Scheme 1).
The highest yields (95e98%) of selenides 1 and 2 were achieved
X
X
CCl (CHCl , C H )
4 3 6 6
Se X2 + 2 HC CH
+
Se
2
o
3
0-40 C
Se
1,2
under the pressure of acetylene (an autoclave, 10e12 atm,
X = Cl (1), Br (2)
ꢁ
3
0e40 C).
Scheme 2. Reactions of selenium monohalides with acetylene.
Thus, we suppose that the statement16a concerning the forma-
tion of (E)-2-chlorovinylselenenyl chloride as the only product of
the reaction of selenium monochloride with acetylene is a mistake.
X
X
CCl (CHCl , CH Cl )
4
3
2
2
SeX2
+
2 HC CH
o
Se
3
0-40 C
16a
To correct these data
are important since they were cited in
X = Cl (1), Br (2)
1,2
5
a,b
reviews
and this may create a wrong notion about the reactivity
Scheme 1. Reactions of selenium dihalides with acetylene.
of acetylene and selenium halides.
Like selenium monochloride, selenium monobromide reacted
with acetylene in carbon tetrachloride or chloroform to afford
selenide 2 in high yield (93%). The precipitation of equimolar
amount of elemental selenium was observed. The reactions of se-
lenium monochloride and monobromide were carried out in an
Although the reactions proceeded faster in polar solvent (ace-
tonitrile, diethyl ether), the yields in these solvents are lower than
in CCl due to the formation of by-products. Along with carbon
tetrachloride, chloroform and methylene chloride were found to be
suitable solvents for the preparation of selenides 1 and 2 in high
yield (80e90%).
First experiments under ambient conditions were carried out by
bubbling acetylene into solutions of selenium dichloride or dibro-
mide in carbon tetrachloride, chloroform or methylene chloride.
These experiments gave selenides 1 and 2, which were contami-
nated with by-products. Apparently, initially formed selenides 1
and 2 underwent further reactions to give mixtures of compounds.
However, satisfactory results were obtained when solutions of
selenium dichloride or dibromide were added to a chloroform
solution saturated with acetylene followed by bubbling acetylene
into this solution. These conditions permitted to obtain selenides 1
and 2 in 30e33% yield with good selectivity. Although these yields
were lower than in experiments under the pressure of acetylene,
the synthetic procedures with the use of acetylene under atmo-
spheric pressure are very valuable since they make selenides 1 and
4
ꢁ
autoclave under the pressure of acetylene (10e12 atm) at 30e40 C
(Scheme 2). The reactions of selenium monochloride and mono-
bromide with acetylene are also suitable for the preparation of
selenides 1 and 2 under atmospheric pressure.
The reaction of selenium dihalides with acetylene represents
efficient atom-economic synthesis of selenides 1 and 2, whereas
a half amount of selenium is lost as precipitate in the case of se-
lenium monohalides.
The stereochemistry of the addition of selenium dihalides to
acetylene can be explained by assuming the formation of in-
termediate selenirenium cations 3 and 4 (Scheme 3). The formation
of selenirenium species as intermediates in the reactions of
3
organylselenenyl halides with alkynes is well known.
X
X
HC CH
+
Se
X
2
easy accessible.
SeX2
Se
The structural assignments of compounds 1 and 2 were made
1
13
77
X
with H, C, Se NMR spectroscopy and GCeMS. (E)-Stereo-
chemistry of selenides 1 and 2 was assigned based on the value of
HC CH
3
the coupling constant 3
J
HH (13.3 Hz), which corresponds to the
trans-position of the protons in 2-halovinyl selenides. It is known
3
X
that the coupling constant
J
HH for (Z)-2-halovinyl selenides is
about 6.3 Hz.1
5c
X
X
Molecular ions of compounds 1 and 2 were
+
Se
observed in the mass spectra.
Se
2 2
The reaction of selenium monochloride, Se Cl , with acetylene
16a
17
was described previously. It is known that arsenic trichloride
reacts with acetylene to afford lewisite, Cl AsCH]CHCl. In a similar
1,2
X
2
X = Cl (1), Br (2)
4
manner, according to the Ref. 16a, selenium monochloride reacts
with acetylene to give (E)-2-chlorovinylselenenyl chloride, ClCH]
CHSeCl. Spectral data for proving the structure of this compound
Scheme 3. A supposed mechanism of the anti-addition of selenium dihalides to
acetylene.

M.V. Musalov et al. / Tetrahedron 68 (2012) 10567e10572
10569
We studied the reactions of selenium tetrahalides with acety-
lene under the pressure in an autoclave as well as under ambient
conditions. In both cases the reactions led to selenides 1 and 2
its dihalo derivatives 1 and 2, the complete change in the direction
of the halogenation reaction is observed. The addition of halogens
to the chalcogen atom of unsaturated chalcogenides rather than to
19
(
45e70% yield) and (E)-2-halovinyl 1,2,2-trihaloethyl selenides (5,
the unsaturated CeC bond is typical for unsaturated tellurides.
6
6
) (15e32% yield) as the main products (Scheme 4). Selenides 5 and
were isolated by column chromatography on silica gel (eluent:
Upon standing for several days at room temperature in chloro-
form solutions, the compounds 7 and 8 underwent spontaneous
rearrangement to selenides 5 and 6 (Scheme 6). The rearrangement
consists of the halogen migration from the selenium atom to the
carbon atoms of the double bond. The reaction can be monitored by
NMR technique.
hexane).
SeO2 + 4 HX
SeX4 + 2 H O
2
X
X
X
X
X
X
CHCl or Et O
3
2
X
X
X
X
X
X
SeX4 + 2HC CH
+
CHCl3
0-25 o
2
0-40 o
C
Se
,2
Se
Se
Se
2
C
1
5,6
X
X
5
,6
X = Cl (1,5), Br (2,6)
7
,8
Scheme 4. Reactions of selenium tetrahalides with acetylene.
X = Cl (5, 8); X = Br (6, 7)
Scheme 6. The rearrangement of compounds 7 and 8.
According to the Ref. 16c, the reaction of acetylene with sele-
nium tetrabromide, which was generated in the system SeO /HBr/
Et O, led to bis(2-bromovinyl)selenium dibromide (7) as a mixture
of (E,E)- and (Z,Z)-isomers (a 1:1.15 ratio) in 54% yield. The authors
reported that they failed to divide (E,E)- and (Z,Z)-isomers on
2
2
Based on this observation (Scheme 6), we suppose that the
reactions of selenium tetrahalides with acetylene (Scheme 4) pri-
marily led to bis(2-halovinyl)selenium dihalides, which underwent
rearrangement to selenides 5 and 6. It is worthy to note that the
reaction of tellurium tetrachloride with acetylene proceeded in
similar manner as anti-addition to afford (E,E)-bis(2-chlorovinyl)
f
a column with silica gel (R was indicated for the mixture of the
f
isomers, i.e., both isomers had the same R ). Only analytical and
NMR 1H data were presented for structural assignment. NMR
data were not given.1
13
C
6c
20
tellurium dichloride.
We studied the reaction of selenium tetrabromide with acety-
lene under the conditions, which were indicated in the Ref. 16c
The compounds 7 and 8 are solids, whereas selenides 5 and 6 are
oils. Interestingly, the rearrangement reactions also occurred when
the crystalline compounds 7 and 8 were allowed to stand on open
air at room temperature. The crystals began ‘weeping’ when the
conversion of solids 7 and 8 into oils 5 and 6 proceeded.
The similar rearrangements with compounds 9 and 10 bearing
different halogen atoms were also observed. However, these re-
actions were concomitant with the formation of by-products and
complex mixtures were formed.
(
a solution of SeO
2
in concentrated HBr was added to a solution
ꢁ
of acetylene in ether at ꢀ78 C). Selenides 2 and 6 were obtained in
4
5% and 32% yields, respectively. The spectral characteristics of
16c
compound 6 were generally the same as those of product 7.
Noteworthy, compounds 6 and 7 have the same composition and
analytical data coincide.
Thus, we suppose that the compound, which was described16c
as a mixture of (E,E)- and (Z,Z)-isomers of compound 7 was, in
Selenides 1 and 2 are novel prospective synthons for organic
synthesis and starting materials for the preparation of organo-
selenium functionalized and heterocyclic compounds. It is known
that vinylic selenides are used for stereoselective synthesis of ethenes
3
fact, selenide 6. Indeed, the values of the coupling constant ( JHH
)
are about 13.3 Hz for (E)-2-halovinyl selenides and 6.3 Hz for (Z)-2-
halovinyl selenides. The value of the coupling constant (3.8 Hz),
16c
which was indicated for compound 7, is too low to be regarded as
3
by cross-coupling reactions. Compounds with the 2-halovinylselanyl
3
JHH for olefinic protons. It became clear why both isomers had the
21
moiety are capable to the nucleophilic substitution of halogen
same R and the authors failed to divide them.
f
atoms, which are activated by the selenium atom via anchimeric
We found that compounds 7e10 can be obtained in almost
quantitative yield by halogenation of selenides 1 and 2. When we
added a solution of bromine or sulfuryl chloride to a solution of
22
assistance.
We found that the addition of selenium dichloride to selenide 1
affords novel five-membered heterocycle, 4,5-dichloro-2-
dichloromethyl-1,3-diselenolane (11), in 80% yield (Scheme 7).
4
selenides 1 and 2 in hexane or CCl , the precipitation of compounds
7
e10 was observed (Scheme 5). Previously unknown compounds 9
and 10 containing different halogen atoms are also accessible by
this approach.
Cl
Cl
Cl
Cl
Cl
Se
Se
MeCN
0–25 °C
SeCl2
+
Se
2
Cl
X
X
X
X
SO Cl or Br
2
2
2
11
1
Se
Se
,2
C H or CCl
Scheme 7. The heterocyclization of selenide 1.
6
14
4
Y
Y
o
0-25 C
1
7-10
This is the first example of heterocyclization of bis(2-halovinyl)
selenides, which demonstrates possibilities of application of sele-
nide 1 in synthesis of heterocyclic compounds.
X = Br, Y = Br (7), X = Cl, Y = Cl (8),
X = Cl, Y = Br (9), X = Br, Y = Cl (10)
Scheme 5. Preparation of compounds 7e10.
3. Conclusion
It is known that divinyl selenide reacted with bromine to give
18
the bromination product of the double bond. In contrast to divinyl
selenide, compounds 1 and 2 underwent the addition of bromine to
the selenium atom (Scheme 5). Thus, going from divinyl selenide to
In conclusion, efficient stereoselective syntheses of compounds
1,2 and 5e10 based on the reactions of selenium dihalides or
monohalides with acetylene have been elaborated. The procedures

10570
M.V. Musalov et al. / Tetrahedron 68 (2012) 10567e10572
are based on cheap and available chemicals (acetylene, selenium,
sulfuryl chloride, bromine), and the products can find application
as starting materials in synthesis of selenium heterocyclic com-
pounds. Thus, the efficient synthesis of novel heterocycle 11 has
been developed from selenide 1 and selenium dichloride. The
previously described reactions of selenium monochloride and tet-
rabromide with acetylene have been reinvestigated. The addition of
(100.6 MHz, CDCl
(76.3 MHz, CDCl
132 (100), 105 (56), 84 (33), 49 (69%).
3
)
108.68 (]CHBr), 120.23 (]CHSe);
d
Se
þ
3
) 388; m/z (EI) 292 [M] (32), 211 (23), 185 (20),
4.3. Reactions of selenium dihalides with acetylene under
atmospheric pressure. Typical procedure
Se
2
Cl
2
to acetylene led to selenide 1 rather than to 2-
A solution of acetylene in CHCl
acetylene into CHCl
ice bath). A solution of selenium dichloride was prepared by stir-
ring a mixture of selenium (1.58 g, 20 mmol) and sulfuryl chloride
3
was obtained by bubbling
(100 mL) for 2 h at 0e5 C (cooling with an
chlorovinylselenenyl chloride. Reactions of selenium tetrachloride
or tetrabromide with acetylene afforded compounds 1 and 5 or 2
and 6. Convenient synthesis of compounds 7e10 in near quanti-
tative yield from selenides 1 and 2 has been developed. Compounds
ꢁ
3
(
2.7 g, 20 mmol) in CHCl
solid disappeared. This usually takes from 30 to 60 min. Then the
mixture was stirred for 15 min and the additional amount of CHCl
3
(1 mL) at ambient temperature until the
7
e10 were found to undergo spontaneous rearrangement with the
migration of the halogens from the selenium atom to the double
bond.
3
(
(
100 mL) was added. The obtained solution of selenium dichloride
20 mmol) in CHCl
3
was added dropwise for 1 h to the solution of
4
4
. Experimental section
.1. General
ꢁ
CHCl
3
saturated with acetylene at 0e5 C (cooling with an ice
bath). During the addition, bubbling of acetylene was continued.
After addition, acetylene was bubbled into the reaction mixture for
ꢁ
3
h at 0e5 C and for 2 h at room temperature. After evaporation of
4 3 2 2 6 6
The solvents (CCl , CHCl , CH Cl , C H , hexane) were dried and
the solvent, the crude product was purified by column chroma-
tography on silica gel (eluent: hexane) to give selenide 1 (1.33 g,
2
3
purified according the literature procedures. Column chromato-
graphic purifications were performed with MachereyeNagel silica
gel (MN Kieselgel 60, 70e230 mesh). Elemental analysis was per-
formed on a Thermo Finnigan EA 1112 elemental analyzer. Melting
points were determined on a Boetius melting point apparatus
33% yield) as a yellowish oil. Selenide 2 was obtained from SeBr
2
and acetylene under the similar conditions in 30% yield.
4.4. Reactions of selenium monohalides with acetylene under
(
PHMK 05 VEB Wagetechnik Rapido, Radebeul, Germany).
The 1H, C and Se NMR spectra were recorded at 400.13,
13
77
a pressure. Typical procedure
1
00.61 and 76.30 MHz, respectively, on a Bruker DPX-400 spec-
1
13
A solution of bromine (1.6 g, 10 mmol) in CHCl
3
(50 mL) was
2
trometer using HMDS as internal standards ( H and C) and Me Se
7
7
added dropwise to a stirred mixture of selenium (1.58 g, 20 mmol)
and CHCl (50 mL) and the resulted mixture was stirred at ambient
as an external standard ( Se). Mass spectra were recorded with
a Shimadzu GCeMS-QP5050A (electronic impact at 70 eV).
Precaution: acetylene can react explosively when combined
with oxygen or other oxidizers. Standard safety measures should be
taken in the working area. Provide adequate explosion-proof
mechanical ventilation to ensure acetylene does not accumulate
and reach its lower explosive limit of 2.5%.
3
temperature until the solid disappeared. This usually takes from 1
to 2 h. Then the mixture was stirred for 15 min. The obtained
solution of selenium monobromide (10 mmol) in CHCl
3
(100 mL)
ꢁ
was heated (30e40 C) in a 1 L rotating autoclave for 5 h under the
pressure of acetylene (10e12 atm). Precipitated selenium (0.79 g)
was filtered off. The solvent was evaporated in vacuo to give the
crude product (2.81 g, 97% yield) as a dark oil. The product 2 (2.70 g,
4
.2. Reactions of selenium dihalides with acetylene under
9
3% yield) of high purity (w99%) was obtained as a yellow oil by
purification by column chromatography on silica gel (eluent: hex-
a pressure. Typical procedure
2 2
ane). Selenide 1 was obtained from Se Cl and acetylene under the
similar conditions in 95% yield.
4
.2.1. (E,E)-Bis(2-chlorovinyl) selenide (1). A solution of sulfuryl
chloride (2.7 g, 20 mmol) in CCl (1 mL) was added dropwise to
4
selenium (1.58 g, 20 mmol) with stirring and the mixture was
stirred at ambient temperature until the solid disappeared. This
usually takes from 30 to 60 min. Then the mixture was stirred for
4.5. Reactions of selenium monohalides with acetylene under
atmospheric pressure. Typical procedure
4
15 min and the additional amount of CCl (140 mL) was added. The
obtained solution of selenium dichloride (20 mmol) was heated
A solution of acetylene in CHCl
acetylene into CHCl
3
was obtained by bubbling
(100 mL) for 2 h at 0e5 C (cooling with an
ꢁ
ꢁ
(
30e40 C) in a 1 L rotating autoclave for 5 h under the pressure of
3
acetylene (10e12 atm). The mixture was filtered and the solvent
was evaporated in vacuo to give the crude product (3.96 g, 98%
yield) as a dark oil. The product 1 (3.64 g, 90% yield) of high purity
ice bath). A solution of sulfuryl chloride (1.35 g, 10 mmol) in CCl
4
(1 mL) was added dropwise to selenium (1.58 g, 20 mmol) with
stirring and the mixture was stirred at ambient temperature
until the solid disappeared. This usually takes from 1 to 2 h.
Then the mixture was stirred for 15 min and the additional
(w99%) was obtained as a yellowish oil by purification by column
chromatography on silica gel (eluent: hexane); [Found: C, 23.51; H,
2
.17; Cl, 35.59; Se, 39.57. C
4
H
4
Cl
2
Se requires: C, 23.79; H, 2.00; Cl,
amount of CHCl
selenium monochloride (10 mmol) in CHCl
3
(100 mL) was added. The obtained solution of
was added dropwise
saturated with acetylene at
3
3
5.11; Se, 39.10]; (400 MHz CDCl
d
H
3
) 6.31 (2H, d, ]CHCl,
(100.6 MHz, CDCl
Se (76.3 MHz, CDCl
EI) 202 [M] (89), 167 (100), 141 (67), 131 (64), 115 (35), 106 (60),
J
3
3
13.3 Hz), 6.63 (2H, d, ]CHSe, J 13.3 Hz);
d
C
3
)
for 1 h to the solution of CHCl
3
ꢁ
117.31 (]CHCl), 121.56 (]CHSe);
d
3
) 336; m/z
0e5 C (cooling with an ice bath). During the addition, bubbling
þ
(
of acetylene was continued. After addition, acetylene was bub-
bled into the reaction mixture for 3 h at 0e5 C and for 3 h at
ꢁ
8
7 (69), 80 (39), 61 (67), 51 (65%).
room temperature. Precipitated selenium was filtered off. After
evaporation of the solvent, the crude product was purified by
column chromatography on silica gel (eluent: hexane) to give
selenide 1 (0.69 g, 34% yield) as a yellowish oil. Selenide 2 was
4
.2.2. (E,E)-Bis(2-bromovinyl) selenide (2). Selenide 2 was obtained
in 95% yield from SeBr
as above; [Found: C, 16.92; H, 1.54; Br, 54.51; Se, 26.89. C
requires: C, 16.52; H, 1.39; Br, 54.95; Se, 27.15]; (400 MHz CDCl
2
and acetylene under the similar conditions
4
H
4
Br Se
2
d
H
3
d
)
obtained from Se
32% yield.
2 2
Br and acetylene under similar conditions in
3
3
6
.43 (2H, d, ]CHBr, J 13.3 Hz), 6.91 (2H, d, ]CHSe, J 13.3 Hz);
C

M.V. Musalov et al. / Tetrahedron 68 (2012) 10567e10572
10571
4
.6. Reactions of selenium tetrahalides with acetylene. Typi-
CDCl
13.7 Hz);
3
) 6.65 (2H, d, ]CHBr, 3J 13.7 Hz), 7.23 (2H, d, ]CHSe, 3
(100.6 MHz, CDCl ) 107.12 (]CHBr), 121.63 (]CHSe).
J
cal procedure
d
C
3
4
.6.1. (E)-2-Chlorovinyl 1,2,2-trichloroethyl selenide (5). Selenide 5
as a yellow oil was obtained in 25% yield along with selenide 1 (71%
yield) from SeCl and acetylene under the same conditions as those
for selenide 6; [Found: C, 17.23; H, 1.65; Cl, 51.47; Se, 29.41.
Cl Se requires: C, 17.61; H, 1.48; Cl, 51.97; Se, 28.94];
400 MHz CDCl
1H, d, 3J 13.3 Hz), 6.88 (1H, d, J 13.3 Hz);
4
.8. 2-Dichloromethyl-4,5-dichloro-1,3-diselenolane (11)
4
A solution of selenium dichloride was prepared by stirring
a mixture of selenium (0.79 g, 10 mmol) and SO Cl (1.35 g,
0 mmol) in acetonitrile (10 mL) at room temperature until the
2
2
C
(
(
H
4 4
4
d
H
1
3
3
3
) 5.32 (1H, d, J 3.4 Hz), 6.03 (1H, d, J 3.4 Hz), 6.67
solid disappeared. This usually takes from 60 to 80 min. The
obtained solution of selenium dichloride (10 mmol) was added
dropwise to a solution of selenide 1 (2.02 g, 10 mmol) in acetoni-
trile (30 mL) and the mixture was stirred at room temperature
for 20 h. The solvent was evaporated in vacuo. The residue was
subjected to column chromatography on silica gel (eluent: hexane/
ether 5:1) to give the product 11 (2.81 g, 80% yield) as a brown oil;
3
d
C
(100.6 MHz, CDCl
3
)
6
2.96 (CHCl), 75.29 (CHCl ), 121.34 (]CHCl), 127.76 (]CHSe).
2
4
.6.2. (E)-2-Bromovinyl 1,2,2-tribromoethyl selenide (6). A solution
(50 mL) was added dropwise
to a stirred mixture of selenium (0.79 g, 10 mmol) and CHCl
50 mL) and the resulted mixture was stirred at ambient temper-
ature until the solid disappeared. This usually takes from 40 to
0 min. Then the mixture was stirred for 15 min. The obtained
of bromine (3.2 g, 20 mmol) in CHCl
3
3
(
[
Found: C,13.38; H,1.28; Cl, 40.69; Se, 44.48. C
3.66; H, 1.15; Cl, 40.31; Se, 44.89]; (400 MHz CDCl
SeCHCl); 5.98 (1H, d, J 8.1 Hz, CHCl ); 5.63 (1H, d, J 8.1 Hz,
SeCHSe); (100.6 MHz, CDCl ) 75.51 (CHCl
6.82 (SeCHSe); Se (76.3 MHz, CDCl
4
4
H Cl
4
Se
2
requires: C,
1
2
d
H
3
) 6.13 (2H, s,
6
2
solution of selenium tetrabromide (0.79 g, 10 mmol) in CHCl
3
was
d
C
3
2
); 66.83 (SeCHCl);
ꢁ
þ
heated (30e40 C) in a 1 L rotating autoclave for 5 h under the
pressure of acetylene (10e12 atm). After evaporation of the solvent,
the crude product was purified by column chromatography on
silica gel (eluent: hexane) to give selenide 2 (1.92 g, 66% yield) and
the product 6 (1.44 g, 32% yield) as a dark yellow oil; [Found: C,
4
2
d
3
) 589; m/z (EI) 352 [M] (33),
69 (66), 256 (12), 221 (16), 195 (10), 173 (15), 160 (82), 141 (41), 115
(25), 106 (37), 93 (27), 80 (36), 61 (100), 36 (34%).
Acknowledgements
10.24; H, 0.94; Br, 71.31; Se, 17.28. C
4
H
4
Br
4
Se requires: C, 10.66; H,
3
0
6
.89; Br, 70.92; Se, 17.52];
d
H
(400 MHz CDCl ) 5.50 (1H, d, J 3 Hz),
.06 (1H, d, J 3 Hz), 6.82 (1H, d, J 14 Hz), 7.11 (1H, d, J 14 Hz);
3
Financial support of the Russian Academy of Sciences (Programs
3
3
3
d
C
5.1.8 and 8.16) and the Russian Foundation for Basic Research
(
100.6 MHz, CDCl
3
) 41.78 (CHBr), 51.42 (CHBr ), 116.43 (]CHBr),
2
(Grants No. 10-03-00543, 11-03-00810 and 12-03-01098) is grate-
125.23 (]CHSe).
fully acknowledged.
References and notes
4
.7. (E,E)-Bis(2-halovinyl)selenium dihalides (7e10)
1. Schwarz, K.; Foltz, C. M. J. Am. Chem. Soc. 1957, 79, 3292.
4
.7.1. (E,E)-Bis(2-bromovinyl)selenium dibromide (7). A solution of
2. (a) Mugesh, G.; du Mont, W.-W.; Sies, H. Chem. Rev. 2001, 101, 2125; (b)
Nogueira, C. W.; Zeni, G.; Rocha, J. B. T. Chem. Rev. 2004, 104, 6255.
bromine (1.6 g, 10 mmol) in hexane (10 mL) was added dropwise to
a stirred solution of selenide 2 (2.91 g, 10 mmol) in hexane (10 mL)
at 0e2 C (an ice bath) for 10 min. The reaction mixture was stirred
for 30 min at 0e2 C and for 1 h at room temperature. The pre-
cipitate was filtered off, washed with cold hexane and dried in
vacuo to give the product 7 as an orange-yellow powder (4.33 g,
9
requires: C, 10.66; H, 0.89; Br, 70.92; Se, 17.52]; (400 MHz CDCl
6
3
. (a) Perin, G.; Lenard a~ o, E. J.; Jacob, R. G.; Panatieri, R. B. Chem. Rev. 2009, 109,
277; (b) Comasseto, J. V.; Ling, L. W.; Petragnani, N.; Stefani, H. A. Synthesis
1
ꢁ
1997, 373; (c) Potapov, V. A.; Amosova, S. V. Russ. J. Org. Chem. 1996, 32, 1142; (d)
Martynov, A. V.; Potapov, V. A.; Amosova, S. V.; Makhaeva, N. A.; Beletskaya, I.
P.; Hevesi, L. J. Organomet. Chem. 2003, 674, 101; (e) Potapov, V. A.; Amosova, S.
V.; Dudareva, G. N.; Shestakova, V. Y.; Zhnikin, A. R.; Petrov, B. V.; Aksamentova,
T. N. Recl. Trav. Chim. Pays-Bas 1996, 115, 443; (f) Potapov, V. A.; Amosova, S. V.;
Petrov, B. V. Phosphorus, Sulfur Silicon Relat. Elem. 1998, 136e138, 587; (g)
Martynov, A. V.; Potapov, V. A.; Amosova, S. V.; Albanov, A. I. Russ. J. Gen. Chem.
ꢁ
6% yield); [Found: C, 10.28; H, 0.84; Br, 71.22; Se, 17.27. C
4 4 4
H Br Se
d
H
3
d
)
2003, 73, 1398.
3
3
.73 (2H, d, ]CHBr, J 13.6 Hz), 7.32 (2H, d, ]CHSe, J 13.6 Hz);
C
4
. (a) Comasseto, J. V. J. Organomet. Chem. 1983, 253, 131; (b) Potapov, V. A.;
Amosova, S. V. Phosphorus, Sulfur Silicon Relat. Elem. 1993, 79, 277; (c) Potapov,
V. A.; Amosova, S. V.; Shestakova, V. Y. Phosphorus, Sulfur Silicon Relat. Elem.
(
100.6 MHz, CDCl ) 106.61 (]CHBr), 121.58 (]CHSe).
3
1
998, 136e138, 205; (d) Amosova, S. V.; Elokhina, V. N.; Nakhmanovich, A. S.;
4
.7.2. (E,E)-Bis(2-chlorovinyl)selenium dichloride (8). Compound 8
Cl as a white
powder under the same conditions as those for selenide 7; [Found:
C, 17.35; H, 1.61; Cl, 52.31; Se, 28.58. C Cl Se requires: C, 17.61; H,
.48; Cl, 51.97; Se, 28.94]; (400 MHz CDCl
3.4 Hz), 7.04 (2H, d, ]CHSe, J 13.4 Hz);
Larina, L. I.; Martynov, A. V.; Steele, B. R.; Potapov, V. A. Tetrahedron Lett. 2008,
49, 974; (e) Potapov, V. A.; Elokhina, V. N.; Larina, L. I.; Yaroshenko, T. I.;
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of Synthesis; Potapov, S. V., Trofimov, B. A., Eds.; Georg Thieme: Stuttgart, 2005;
Vol. 24, p 957; (g) Comasseto, J. V.; Ferreira, J. T. B.; Petragnani, N. J. Organomet.
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5. (a) Back, T. G. In Organoselenium Chemistry; Liotta, D., Ed.; John Wiley: New
York, NY, 1987; p 1; (b) Magnus, P. D. In Comprehensive Organic. Chemistry;
Barton, D., Ollis, W. D., Jones, D. N., Eds.; Pergamon: Oxford, 1979; Vol. 3, p 520;
was obtained in 98% yield from selenide 1 and SO
2
2
4
H
4
4
3
1
1
d
H
3
) 6.62 (2H, d, ]CHCl, J
(100.6 MHz, CDCl
3
d
C
3
)
119.35, 119.79.
(c) Shmid, G. H. In The Chemistry of the CarboneCarbon Triple Bond; Patai, S., Ed.;
John Wiley: Chichester, U.K., 1978; p 275.
4
.7.3. (E,E)-Bis(2-chlorovinyl)selenium dibromide (9). Compound 9
6
. (a) Campbell, T. W.; Walker, H. G.; Coppinger, G. M. Chem. Rev. 1952, 50, 279; (b)
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was obtained in 97% yield from selenide 1 and bromine as an
orange-yellow powder under the same conditions as those for
selenide 7; [Found: C, 12.89; H, 0.97; Cl, 19.21; Br, 44.62; Se, 22.25.
7
C
2
(
H
4 4
Cl
1.83];
2H, d, ]CHSe, J 13.4 Hz);
2 2
Br Se requires: C, 13.28; H, 1.11; Cl, 19.60; Br, 44.18; Se,
3
d
H
(400 MHz CDCl
3
) 6.56 (2H, d, ]CHCl, J 13.4 Hz), 7.00
(100.6 MHz, CDCl ) 118.77, 119.34.
3
d
C
3
8. (a) Amosova, S. V.; Penzik, M. V.; Albanov, A. I.; Potapov, V. A. Tetrahedron Lett.
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4
1
.7.4. (E,E)-Bis(2-bromovinyl)selenium dichloride (10). Compound
0 was obtained in 98% yield from selenide 2 and SO Cl as a white
powder under the same conditions as those for selenide 7; [Found:
C, 13.41; H, 1.03; Cl, 19.87; Br, 43.98; Se, 22.17. C Cl Br Se re-
quires: C, 13.28; H, 1.11; Cl, 19.60; Br, 44.18; Se, 21.83]; (400 MHz
2
2
2009, 79, 161.
4
H
4
d
2
2
9
. (a) Potapov, V. A.; Amosova, S. V.; Volkova, K. A.; Penzik, M. V.; Albanov, M. V.
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2
1
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