Effect of the chalcogen nature on the reaction of propane-1,3- dichalcogenolates with 2,3-dichloroprop-1-ene

Article abstract of DOI:10.1134/S1070428014010023

The direction of the reaction of propane-1,3-dichalcogenolates with 2,3-dichloroprop-1-ene in the system hydrazine hydrate-KOH depends not only on the conditions but to a greater extent on the chalcogen nature. Dipotassium propane-1,3-dithiolate and propane-1,3-diselenolate give rise to products of substitution of the chlorine atom on the sp ³-carbon atom, which are capable of undergoing further transformations (domino reaction). Dipotassium propane-1,3-ditellurolate promotes elimination of both chlorine atoms with formation of allene.

Full text of DOI:10.1134/S1070428014010023

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2014, Vol. 50, No. 1, pp. 6–12. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © E.P. Levanova, V.A. Grabel’nykh, V.S. Vakhrina, N.V. Russavskaya, A.I. Albanov, L.V. Klyba, N.A. Korchevin, I.B. Rozentsveig,
2014, published in Zhurnal Organicheskoi Khimii, 2014, Vol. 50, No. 1, pp. 14–20.
Effect of the Chalcogen Nature on the Reaction
of Propane-1,3-dichalcogenolates with 2,3-Dichloroprop-1-ene
E. P. Levanova, V. A. Grabel’nykh, V. S. Vakhrina, N. V. Russavskaya, A. I. Albanov,
L. V. Klyba, N. A. Korchevin, and I. B. Rozentsveig
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
e-mail: venk@irioch.irk.ru
Received July 3, 2013
Abstract—The direction of the reaction of propane-1,3-dichalcogenolates with 2,3-dichloroprop-1-ene in the
system hydrazine hydrate–KOH depends not only on the conditions but to a greater extent on the chalcogen
nature. Dipotassium propane-1,3-dithiolate and propane-1,3-diselenolate give rise to products of substitution of
the chlorine atom on the sp3-carbon atom, which are capable of undergoing further transformations (domino
reaction). Dipotassium propane-1,3-ditellurolate promotes elimination of both chlorine atoms with formation
of allene.
DOI: 10.1134/S1070428014010023
tion of allene and elemental tellurium [7]. The reac-
tions of benzenechalcogenolate ions PhY– (Y = S, Se)
with dichloropropene II in the system hydrazine
hydrate–KOH at 30–35°C gave mixtures of several
products resulting from domino reaction which in-
cluded replacement of the Csp3–chlorine atom, dehy-
drochlorination of the substitution product with forma-
tion of allenyl chalcogenide, and allene–acetylene
rearrangement. Raising the temperature to 60°C
induced one more step of the domino reaction,
addition of PhY– to the acetylene derivative [9, 10].
Thus, it is difficult to predict a priori the way in which
propane-1,3-dichalcogenolates Ia–Ic would react with
2,3-dichloroprop-1-ene (II), and study of this reaction
should favor development of theoretical concepts
concerning the effect of the structure of chalcogen-
containing nucleophile, primarily of the chalcogen
nature, on the reaction direction.
Propane-1,3-dichalcogenolates Ia–Ic are widely
used in the synthesis of various organochalcogen com-
pounds. Thiacrown ethers were synthesized from
propane-1,3-ditiolate Ia [1], whereas propane-1,3-di-
selenolate Ib was used to prepare stable organosele-
nium-bridged cyclodextrins with hydrophobic cavities,
capable of forming host–guest complexes [2], as well
as selenium-containing calixarene derivatives [3]. Al-
kylation of dichalcogenolates Ia–Ic with alkyl halides
produced 1,3-bis(alkylchalcogeno)propanes [4, 5]
which can act as efficient ligands in the complexation
with transition metal ions to afford novel homoge-
neous catalysts [6].
The present article reports on the synthesis of
organochalcogen compounds via reaction of dichalco-
genolates Ia–Ic with 2,3-dichloroprop-1-ene (II).
Compound II is an electrophilic agent whose molecule
contains two chlorine atoms attached to differently
hybridized carbon atoms. We previously showed
[7–10] that the direction of the reaction of dichloro-
propene II with chalcogen-containing nucleophiles
strongly depends on the chalcogen nature, as well as
on the conditions. Dichalcogenide ions Y22– (Y = S, Se)
reacted with dichloropropene II via replacement of the
chlorine atom attached to the sp3-carbon atom [7, 8].
Ditelluride ion Te22– promoted elimination of both
chlorine atoms as chloride ions, leading to the forma-
Propane-1,3-dichalcogenolates Ia–Ic were prepared
by reductive cleavage of poly(trimethylene dichalco-
genides) which were synthesized in turn from
1-bromo-3-chloropropane and elemental chalcogens
preliminarily activated in the system hydrazine hy-
drate–alkali to generate the corresponding dichalco-
genide ions Y22– (Y = S, Se, Te) [4, 5, 11]. Oligomeric
poly(trimethylenedichalcogenides) were reduced in
the system hydrazine hydrate–KOH as shown in
6

EFFECT OF THE CHALCOGEN NATURE ON THE REACTION OF PROPANE-1,3-...
7
Scheme 1. To complete the reaction, we used 2.5 equiv
of potassium hydroxide with respect to the stoichio-
metric amount [12].
ular nucleophilic addition of the thiolate ion to the
triple bond leads to 1,4-dithiepine IIIa. Compound
IIIa can also be formed as a result of intramolecular
Markovnikov addition of the thiolate ion to the allene
fragment of sulfide B.
Scheme 1.
N2H4·H2O, KOH
The reaction of dithiolate Ia with dichloride II was
accompanied by side formation of 1,3-bis(2-chloro-
prop-2-en-1-ylsulfanyl)propane (IVa) and 1-allenyl-
sulfanyl-3-(2-chloroprop-2-en-1-ylsulfanyl)propane
(Va) in an overall yield of ~10% (Scheme 4). The
formation of IVa and Va may be regarded as some
support for the proposed reaction scheme.
Y
Y
KY
YK
–N2, –H2O
n
Ia–Ic
n = 5–12 [4, 5, 11]; Y = S (a), Se (b), Te (c).
Propane-1,3-dichalcogenolates Ia–Ic thus obtained
were brought (without isolation) into reaction with
2,3-dichloroprop-1-ene (II). Dipotassium propane-1,3-
dithiolate (Ia) reacted with an equimolar amount of
2,3-dichloroprop-1-ene (II) at 30–35°C to give
2-methyl-6,7-dihydro-5H-1,4-dithiepine (IIIa) as the
major product (yield 46%; Scheme 2).
The yield of open-chain compounds IVa and Va
insignificantly increased (overall yield ~15%) when
the reaction of Ia with II was carried out at a reactant
ratio of 1:2, whereas the yield of cyclic product IIIa
decreased to 38%. Raising the temperature to 60°C had
almost no effect on the yield of IIIa (47%). The reac-
tion of propanedithiolate Ia with 2 equiv of dichloro-
propene II at 0°C gave 48% of IVa, ~5% of Va, and 3–
5% of IIIa. Thus, unlike benzenechalcogenolates PhY–
(Y = S, Se) [9, 10], the reaction of propanedithiolate Ia
with dichloride II even at 0°C involves all steps of the
domino process. Under these conditions, only products
of substitution of the allylic chlorine atom were
obtained from benzenechalcogenolates (first step of the
domino reaction) [9, 10].
Scheme 2.
S
H2C
Cl
Ia
+
Me
–2KCl
Cl
S
II
IIIa
The formation of compound IIIa was rationalized
with account taken of the data in [9, 10] by the
following transformation sequence (Scheme 3). In the
first step, nucleophilic replacement of the allylic
chlorine atom in II yields sulfide A which undergoes
dehydrochlorination to allenyl sulfide B by the action
of alkali present in the reaction mixture. Allene–acety-
lene rearrangement of intermediate B gives acetylenic
sulfide C, and cyclization of the latter via intramolec-
The observed acceleration of the other steps of the
domino reaction with nucleophile Ia as compared to
PhS– may be rationalized in terms of a probable mech-
anism of dehydrochlorination with formation of allene
derivative. Insofar as that step involves elimination of
chlorine from the sp2-carbon atom, the most probable
Scheme 3.
Me
H2C
OH–
–Cl–, –H2O
S–
·
S
S–
S
Ia
+ II
H2C
–KCl
S
S–
Cl
A
B
C
S
S
H2O
H2O
–OH–
IIIa
–OH–
S
S
CH2
Me
Scheme 4.
H2C
CH2
CH2
S
S
·
S
S
A
+
II
B + II
–Cl–
–HCl
–Cl–
H2C
Cl
Cl
Cl
IVa
Va
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 1 2014

LEVANOVA et al.
8
mechanism of elimination of HCl is E1cB with inter-
mediate formation of carbanion D by the action of
alkali (Scheme 5).
compounds IIIb, IVb, and Vb. Unexpectedly, 1,2-di-
selenolane (VI) was isolated, though it was not detect-
ed in the reaction mixture by the end of the process.
Poly(trimethylenediselenide) (VIIa) separated from
the distillation products on storage. Like poly(tri-
methyleneditelluride) (VIIb) [5], oligomer VIIa is
converted into the monomer by the action of organic
solvents and then into 1,2-diselenolane (VI). Oligomer
VIIa is likely to be formed as a result of thermal
decomposition of compounds IVb and Vb in the
distillation flask (Scheme 8). 1,2-Diselenolane (VI)
was described previously [4], and the spectral param-
eters of the product isolated by us were fully consistent
with published data.
Scheme 5.
H2C
OH–
H2C
SR
SR
–H2O
Cl
Cl
D
·
SR
–Cl–
H2C
If R = Ph, the PhS substituent should stabilize
structure D to a greater extent as compared to
SCH2CH2CH2S–. However, the observed opposite pat-
tern suggests intramolecular generation of the corre-
sponding carbanion according to Scheme 6 (anchi-
meric assistance). The transformation E → IIIa is
likely to be fairly fast.
Scheme 8.
Se
Se
Se
IVb or Vb
n
Se
VI
VIIa
Scheme 6.
Compound IVb was formed as virtually the only
product in the reaction carried out at 0°C (11 h; yield
89%), and we succeeded in isolating it by vacuum
distillation. In this case, only traces of allene derivative
Vb were detected.
H2C
H
S
·
S
SH
Cl
–Cl–
H2C
H
S
E
IIIa
Interestingly, in no case acetylenic derivatives
VIIIa and VIIIb were detected among the products in
the reactions of propanedichalcogenolates Ia and Ib
with dichloropropene II, whereas the corresponding
compounds were obtained in 23 and 58% yield in the
reactions with PhS– and PhSe–, respectively [9, 10].
In the reaction of propane-1,3-diselenolate (Ib)
with dichloropropene II (molar ratio 1:2; 30–35°C) we
obtained 27% of 1,3-bis(2-chloroprop-2-en-1-yl-
selanyl)propane (IVb) (Scheme 7). Cyclic product,
2-methyl-6,7-dihydro-5H-1,4-diselenepine (IIIb), was
formed in trace amount (yield ~1%) and was identified
only by GC/MS (m/z 242 [M]+· for 80Se). By IR spec-
troscopy (νC=C=C 1941 cm–1) and GC/MS we also
identified among the products 1-allenylselanyl-3-(2-
chloroprop-2-en-1-ylselanyl)propane (Vb, ~3%).
Me
CH2
Y
Y
Cl
VIIIa, VIIIb
Y = S (a), Se (b).
Scheme 7.
Compounds like VIII are products of the allene–
acetylene rearrangement which also follows carbanion
mechanism [13]. Presumably, just in this case better
stabilization of intermediate carbanion by the PhY
substituent is crucial.
H2C
CH2
Me
Se
Se
Ib
+ II
Cl
Cl
IVb
Se
The mass spectrum of IVb contained no molecular
ion peak. Its fragmentation pattern conforms to the
scheme proposed previously [4] for 1,3-bis(alkyl-
selanyl)propanes, where the main decomposition
pathway of the molecular ion involves cleavage of the
Se–C3H4Cl bond. The resulting ion is likely to have
cyclic structure F due to intramolecular substitution.
CH2
·
Se
Se
+
+
H2C
Cl
Se
IIIb
Vb
We failed to isolate individual compounds by
vacuum distillation of the product mixture containing
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 1 2014

EFFECT OF THE CHALCOGEN NATURE ON THE REACTION OF PROPANE-1,3-...
9
Scheme 9.
[C3H4Cl]+
m/z 75 (3%)
m/z 93
(6%)
[C3H3Se]+
+·
+·
Se
H2C
Cl
F, m/z 277 (29%)
H2C
CH2
m/z 119 (4%)
Se
Se
Se
–C3H4Cl·
–C3H4Cl·
Se Se
Cl
Cl
[Se2]+·
–C3H6
IVb, [M]+· 352 (0%)
G, m/z 202 (46%)
m/z 160 (11%)
Such process is typical of unbranched thiols [14]
(Scheme 9; m/z values for 80Se and 35Cl isotopes are
given).
reaction mixture contained no products of chlorine
replacement by tellurium-containing group. According
1
to the H and 13C NMR data, allene was formed
without impurities of methylacetylene or propene. The
process was accompanied by regeneration of tellurocol
VIIb (up to 70%). In addition, elemental tellurium
precipitated on storage from the aqueous hydrazine
solution after separation of VIIb. The amount of
elemental tellurium was ~20% of its overall amount in
the initial compound VIIb taken for the generation of
ditellurolate Ic according to Scheme 1.
The molecular ion of Vb (which is also absent in
the mass spectrum) decomposes along two pathways,
with elimination of C3H4Cl· and C3H3· radicals and
formation of cyclic ions F and H, respectively
(Scheme 10). Further fragmentation of F and H yields
the same ion G, and the latter decomposes in a way
similar to that shown in Scheme 9, which corresponds
to the mass spectrum of 1,2-diselenolane (VI) [4]. The
formation of ions F, H, and [C3H3Se]+ (m/z 119) may
be regarded as an indirect support for the assumed
structure of Vb.
Unlike sulfur and selenium analogs, the reaction of
propane-1,3-ditellurolate (Ic) with dichloropropene II
involves halophilic attack by anion Ic on the 2-chlorine
atom in II (see [15]; Scheme 12). Dianion XI then
reacts with dichloropropene II, ensuring chain prop-
agation and eventually leading to oligomer VIIb
through dianion XIII (Scheme 13).
Propane-1,3-ditellurolate (Ic) reacted with dichloro-
propene II only through elimination of both chlorine
atoms with formation of allene (IX) which was isolat-
ed in 77% yield (Scheme 11). When the reaction was
carried out at 40–50°C, vigorous evolution of allene
(IX) was observed simultaneously with the addition of
dichloropropene II. Lowering the temperature to 25°C
resulted in reduced rate of allene evolution, but the
Some amount of anions like XI or XIII remains in
the aqueous hydrazine solution after separation of tel-
lurocol VIIb; like many organic ditellurides [16], these
anions decompose with liberation of elemental tellu-
Scheme 10.
[C3H3Se]+
m/z 119 (8%)
[C3H4Cl]+
m/z 75 (4%)
[CHSe]+
m/z 93 (10%)
CH2
–C3H4Cl·
–C3H3
·
Se
·
Se
+·
CH2
·
Se
Se
H, m/z 241 (20%)
F, m/z 277 (7%)
G, m/z 202 (35%)
H2C
Cl
Vb, [M]+· 316 (0%)
·
–C3H3
–C3H4Cl·
[Se2]+·
m/z 160 (16%)
Scheme 11.
Te
Te
Ic
+
II
+
·
H2C
CH2
–2KCl
n
VIIb
IX
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 1 2014

LEVANOVA et al.
10
Scheme 12.
H2C
Cl
Ic
Te–
Cl
Te
IX
+
–Te
TeCl
–Te
Te
–Cl–
–Cl–
II
X
XI
–Te
Te–
Ic
Scheme 13.
Te
TeCl
Te–
–Te
Te
XI
+
II
IX +
–Cl–
XII
Ic
–Cl–
–Te
Te
Te
Te
Te
XIII
rium. Tellurium-containing anions present in the
aqueous hydrazine solution are partly converted into
1,2-ditellurolane (cf. [5]) upon treatment with organic
solvents.
temperature 250°C; carrier gas helium, flow rate
0.7 mL/min; oven temperature programming from 60
to 260°C at a rate of 15 deg/min; detector temperature
250°C; quadrupole mass analyzer; electron impact,
70 eV; ion source temperature 200°C; a.m.u. range
34–650).
Thus, the chalcogen nature essentially affects the
reaction of propane-1,3-dichalcogenolates Ia–Ic with
2,3-dichloroprop-1-ene (II). Sulfur and selenium in
dianions Ia and Ib favor substitution of the allylic
chlorine atom and promote further transformations at
a temperature higher than 25°C. Propane-1,3-ditel-
lurolate (Ic) give rise only to elimination product. The
observed effect of the chalcogen nature is consistent
with specific reactivity of organotellurium compounds
[17], as well as with variation of the properties of
elements and compounds derived therefrom according
to Mendeleev’s Periodic Law.
2-Methyl-6,7-dihydro-5H-1,4-dithiepine (IIIa).
A solution of 15.1 g (270 mmol) of potassium hydrox-
ide in 70 mL of hydrazine hydrate was heated to 50–
60°C, 5.7 g (54 mmol) of poly(trimethylene disulfide)
prepared as described in [11] was added, the mixture
was stirred for 2 h at 85–90°C and cooled to 30°C, and
6.0 g (54 mmol) of 2,3-dichloroprop-1-ene (II) was
added dropwise at 30–35°C. The mixture was stirred
for 3 h at that temperature, cooled to 25°C, treated
with 50 mL of water, and extracted with methylene
chloride (3× 50 mL). The combined extracts were
dried over anhydrous MgSO4 and evaporated, and the
residue was distilled under reduced pressure. Yield
46%, bp 65–66°C (2.5 mm). IR spectrum, ν, cm–1:
2997, 2966, 2927, 2908, 2843, 1592, 1568, 1429,
1413, 1373, 1301, 1256, 1156, 1093, 1033, 1011, 978,
937, 910, 867, 815, 771, 746, 689, 660, 607, 459.
EXPERIMENTAL
The initial 2,3-dichloroprop-1-ene and reaction
products were analyzed by GLC on an LKhM 80-
MD-2 chromatograph using a 2000×3-mm column
packed with 5% XE-60 on Chromaton N-AW-HMDS
(linear oven temperature programming from 30 to
230°C at a rate of 12 deg/min; carrier gas helium). The
IR spectra were measured from thin films on a Bruker
4
1H NMR spectrum, δ, ppm: 1.88 d (3H, Me, J =
1.0 Hz), 2.13 quint (2H, 6-H, 3J = 6.0 Hz), 3.37 t (2H,
3
3
5-H, J = 6.0 Hz), 3.41 t (2H, 7-H, J = 6.0 Hz),
5.71 br.q (1H, 3-H, J = 1.0 Hz). 13C NMR spectrum,
4
1
IFS-25 spectrometer. The H, 13C, and 77Se NMR
δC, ppm: 26.31 (Me), 31.40 (C6), 31.52 (C7), 31.70
(C5), 114.91 (C3), 131.99 (C2). Mass spectrum, m/z
(Irel, %): 146 (19) [M]+·, 131 (1) [M – Me]+, 117 (8)
[M – C2H5]+, 113 (2) [M – SH]+, 106 (5) [C3H6S2]+·,
105 (3), 84 (3) [C4H4S]+·, 79 (3) [MeS2]+, 73 (7)
[C3H5S]+, 72 (4), 71 (6), 64 (4) [S2]+·, 59 (8) [C2H3S]+,
49 (7) [MeSH2]+. Found, %: C 48.80; H 6.87; S 44.11.
C6H10S2. Calculated, %: C 49.27; H 6.89; S 43.84.
M 146.27.
spectra were recorded on a Bruker DPX-400 spectrom-
eter at 400.13, 100.61, and 76.31 MHz, respectively;
CDCl3 was used as solvent; the chemical shifts were
determined relative to tetramethylsilane (1H, 13C) or
Me2Se (77Se) as reference.
The mass spectra were obtained on a Shimadzu
GCMS-QP5050A instrument (SPB-5 capillary column,
60 000 ×0.25 mm, film thickness 0.25 μm; injector
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 50 No. 1 2014

EFFECT OF THE CHALCOGEN NATURE ON THE REACTION OF PROPANE-1,3-...
11
1,2-Diselenolane (VI). Vacuum distillation of the
residue obtained after evaporation of the extract gave
two fractions boiling at 150–157°C (2.5 mm) and 157–
170°C (2.5 mm). Yellow crystals of oligomer VIIa
separated from these fractions on storage. Yield 0.36 g
(7% calculated on the initial selenocol). The NMR
spectra of a solution of these crystals in CDCl3 were
identical to those given in [4].
1,3-Bis(2-chloroprop-2-en-1-ylsulfanyl)propane
(IVa). Poly(trimethylene disulfide), 5.2 g (49 mmol),
was dissolved in a mixture of 61 mL of hydrazine
hydrate and 13.7 g (245 mmol) of potassium hydrox-
ide, the mixture was cooled to 0°C, 10.9 g (98 mmol)
of dichloropropene II was added dropwise at that tem-
perature, and the mixture was stirred for 10 h at 0°C
and then treated as described above. Yield 48%,
bp 142–143°C (2 mm). IR spectrum: ν 1627 cm–1
Allene (IX). A solution of 4.55 g (81 mmol) of
potassium hydroxide in 20 mL of hydrazine hydrate
was prepared in a conical flask using a magnetic
stirrer. The solution was heated to 85°C, 4.82 g
(16 mmol) of tellurocol prepared as described in [5]
was added, the mixture was cooled to 25°C, and the
system was connected to two traps, one of which was
cooled to –30°C, and the other, to –85°C. The mixture
was heated to 40°C, and 3.6 g (32 mmol) of dichloro-
propene II was added dropwise. The second trap
collected 1.0 g (77%) of allene (IX) whose spectral
parameters were identical to those reported in [7].
When allene no longer evolved, 3.4 g of tellurocol
(VIIb) was filtered off from the reaction mixture; it
was identical to a sample described in [5]. After
separation of tellurocol, 0.83 g of elemental tellurium
precipitated from the mother liquor.
1
(C=C). H NMR spectrum, δ, ppm: 1.85 quint (2H,
3
3
СCH2C, J = 7.1 Hz), 2.61 t (4H, SCH2CC, J =
7.1 Hz), 3.35 s (4H, SCH2CCl=), 5.28 s and 5.36 s
(4H, H2C=). 13C NMR spectrum, δC, ppm: 28.29
(CCH2S), 30.17 (SCH2CC), 39.75 (SCH2CCl=),
114.29 (H2C=), 138.48 (–CCl=). Mass spectrum, m/z:
256 [M]+ (35Cl), very low intensity; 183 [M – 75]+
(37Cl), 181 [M – 75]+ (35Cl). Found, %: C 42.02;
H 5.59; Cl 27.28; S 24.90. C9H12Cl2S2. Calculated, %:
C 42.02; H 5.49; Cl 27.56; S 24.93. M 257.24
According to the GLC, 1H NMR, and GC/MS data,
the fraction with bp 135–140°C (2 mm) contained
~10% of 1-allenylsulfanyl-3-(2-chloroprop-2-en-1-yl-
sulfanyl)propane (Va), which was not isolated as
individual substance. IR spectrum: ν 1941 cm–1
(C=C=C). Mass spectrum, m/z: 220 [M]+· (35Cl), 185
[M – Cl]+, 145 [M – 75]+.
This study was performed using the facilities of
the Baikal Joint Analytical Center, Siberian Branch,
Russian Academy of Sciences.
1,3-Bis(2-chloroprop-2-en-1-ylselanyl)propane
(IVb). A solution of 9.82 g (175 mmol) of potassium
hydroxide in 45 mL of hydrazine hydrate was heated to
50–60°C, 7.0 g (35 mmol) of selenocol (prepared as
described in [4]) was added, the mixture was stirred for
2 h at 85–90°C and cooled to 0°C, and 7.8 g
(70 mmol) of dichloropropene II was added. The mix-
ture was stirred for 11 h at 0°C, allowed to warm up to
room temperature, treated with 50 mL of water, and
extracted with methylene chloride (3×50 mL). The
combined extracts were dried over MgSO4 and
evaporated, and the residue was distilled under reduced
pressure, a fraction boiling at 148–150°C (2.5 mm)
being collected. IR spectrum: ν 1623 cm–1 (C=C).
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va, E.R., Albanov, A.I., Korotaeva, I.M., Toryashino-
va, D.S.D., and Korchevin, N.A., Russ. J. Gen. Chem.,
2006, vol. 76, 726.
6. Bayon, J.C., Claver, C., and Masdeu-Bulto, A.M., Coord.
Chem. Rev., 1999, vols. 193–195, p. 73.
7. Levanova, E.P., Grabel’nykh, V.A., Russavskaya, N.V.,
Klyba, L.V., Zhanchipova, E.R., Albanov, A.I., Taraso-
va, O.A., and Korchevin, N.A., Russ. J. Gen. Chem.,
2009, vol. 79, p. 1097.
1H NMR spectrum, δ, ppm: 2.00 quint (2H, CCH2C,
2
3JH–Se = 7.2 Hz), 2.68 t (4H, SeCH2CC, JSe–H
=
2
4.5 Hz), 3.41 s (4H, SeCH2C=C, JH–Se = 13.9 Hz),
5.22 s and 5.31 s (4H, CH2=). 13C NMR spectrum, δC,
1
ppm: 23.99 (SeCH2CC, JC–Se = 64.3 Hz), 30.07
(CCH2C), 30.69 (SeCH2C=C, 1JC–Se = 67.3 Hz), 113.66
(CH2=), 139.23 (=CCl). 77Se NMR spectrum, δSe, ppm:
203.87. (For mass spectrum, see text). Found, %:
C 30.72; H 4.01; Cl 19.77; Se 44.63. C9H14Cl2Se2.
Calculated, %: C 30.79; H 4.02; Cl 20.20; Se 44.99.
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LEVANOVA et al.
12
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