Synthesis of bis(2-haloalkyl) selanes and selenides based on selenium dioxide and terminal alkenes

Article abstract of DOI:10.1134/S1070428017120041

Selenium tetrahalides generated from selenium dioxide and hydrogen halides (HCl, HBr) reacted with hex-1-ene, hept-1-ene, and oct-1-ene at a SeO₂?alkene molar ratio of 1: 2 to give mixtures of dihalobis-(2-haloalkyl)-λ⁴-selanes (yield 80?90%) and bis(2-haloalkyl) selenides (yield 5?12%). Halogenation of the resulting mixtures afforded 85?93% (calculated on the initial SeO₂) of the corresponding dihalobis(2-haloalkyl)-λ⁴-selanes, and the reduction of the same mixtures with Na₂S₂O₅ gave bis(2-haloalkyl) selenides in 80?86% yield. In the reaction with a SeO₂?alkene ratio of 5: 8, pure dihalobis(2-haloalkyl)-λ⁴-selanes were formed in 84?93% yield. Dichlorobis(2-chloro-2-phenylethyl)-λ⁴-selane was obtained in 72% yield in the reaction of SeO₂?HCl with styrene.

Full text of DOI:10.1134/S1070428017120041

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2017, Vol. 53, No. 12, pp. 1809–1814. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © M.V. Musalov, E.O. Kurkutov, V.A. Potapov, A.G. Khabibulina, A.I. Albanov, S.V. Amosova, 2017, published in Zhurnal
Organicheskoi Khimii, 2017, Vol. 53, No. 12, pp. 1774–1779.
Synthesis of Bis(2-haloalkyl) Selanes
and Selenides Based on Selenium Dioxide
and Terminal Alkenes
M. V. Musalov, E. O. Kurkutov, V. A. Potapov, A. G. Khabibulina,
A. I. Albanov, and S. V. Amosova*
Favorskii Irkutsk Institute of Chemistry, Siberian Branch, Russian Academy of Sciences,
ul. Favorskogo 1, Irkutsk, 664033 Russia
*e-mail: amosova@irioch.irk.ru
Received August 15, 2017
Abstract—Selenium tetrahalides generated from selenium dioxide and hydrogen halides (HCl, HBr) reacted
with hex-1-ene, hept-1-ene, and oct-1-ene at a SeO2‒alkene molar ratio of 1:2 to give mixtures of dihalobis-
(2-haloalkyl)-λ4-selanes (yield 80‒90%) and bis(2-haloalkyl) selenides (yield 5‒12%). Halogenation of the
resulting mixtures afforded 85‒93% (calculated on the initial SeO2) of the corresponding dihalobis(2-halo-
alkyl)-λ4-selanes, and the reduction of the same mixtures with Na2S2O5 gave bis(2-haloalkyl) selenides in 80‒
86% yield. In the reaction with a SeO2‒alkene ratio of 5:8, pure dihalobis(2-haloalkyl)-λ4-selanes were formed
in 84‒93% yield. Dichlorobis(2-chloro-2-phenylethyl)-λ4-selane was obtained in 72% yield in the reaction of
SeO2‒HCl with styrene.
DOI: 10.1134/S1070428017120041
There are a few published data on the addition re-
actions of selenium tetrahalides with terminal alkenes,
and no NMR spectra of the addition products were
given in these publications [1, 2]. Instead of using
solid selenium tetrahalides that are poorly soluble in
most organic solvents, they are generated in situ from
SeO2 and hydrogen halides [2–4]. The reactions of
ethylene, hex-1-ene, and styrene with a mixture of
SeO2 and HX (X = Cl, Br) afforded dihalobis(2-halo-
ethyl)-λ4-selanes, dichlorobis(2-chlorohexyl)-λ4-
selane, and dihalobis(2-halo-2-phenylethyl)-λ4-selanes,
respectively [2]. However, Migalina et al. [3] studied
the reactions of SeO2‒HX (X = Cl, Br) with styrene
and its derivatives and obtained products of halogen
addition to the double bond, whereas no selenium
tetrahalide adducts to the double bond were formed.
The use of new electrophilic reagents, selenium
dihalides, opens new prospects in the synthesis of
organoselenium compounds [5–15]. The addition of
selenium dibromide to terminal alkenes leads to the
formation of bis(2-bromoalkyl)selanes in 95‒100%
yield [13, 14]. Selenium dibromide reacted with hex-1-
ene and oct-1-ene to give kinetically controlled anti-
Markovnikov intermediates, bis(1-bromoalkan-2-yl)
selenides, which underwent fast rearrangement
(presumably, through seleniranium intermediates) to
thermodynamically stable Markovnikov adducts [13].
Halogenation of bis(2-haloalkyl) selenides afforded
95–98% of dihalobis(2-haloalkyl)-λ4-selanes [14].
Reactions of selenium tetrahalides with alkenes
require further detailed studies with the aid of NMR
spectroscopy to determine the structure of interme-
Scheme 1.
SeO2
+
4HX
SeX4
+
2H2O
R
Et2O–H2O
0 to 20–25°C
R
R
R
Se
Se
SeX4
+
2
+
R
CH2
X
X
X
X
X
X
1–6
7–12
1–3, 7–9, X = Cl; 4–6, 10–12, X = Br; 1, 4, 7, 10, R = C4H9; 2, 5, 8, 11, R = C5H11; 3, 6, 9, 12, R = C6H13.
1809

MUSALOV et al.
1810
Scheme 2.
X
R
X
X
R
X
R
R
SeX4
+ 2
R
CH2
R
X–
Se
R
R
Se
Se
X
X
X
X
X
X
X
13–18
R
R
Se
R
X–
Se
X
X
X
X
X
X
X
1–6
13–15, X = Cl; 16–18, X = Br; 13, 16, R = C4H9; 14, 17, R = C6H13; 15, 18, R = C5H11.
diates and reaction products. In this work we studied
the addition of selenium tetrahalides generated from
SeO2 and hydrogen halides to terminal alkenes (hex-
1-ene, hept-1-ene, and oct-1-ene) at a SeO2‒alkene
ratio of 1:2. These reactions led to the formation of
mixtures of dihalobis(2-haloalkyl)-λ4-selanes 1–6 and
bis(2-haloalkyl) selenides 7–12 in 80‒90 and 5‒12%
yields, respectively (according to the NMR data;
Scheme 1).
15 are formed as intermediate products which readily
rearrange to more stable Markovnikov adducts 1‒3
(Scheme 2). This rearrangement is analogous to the
transformation of bis(1-haloalkan-2-yl) selenides to bis-
(2-haloalkyl) selenides described by us previously [13].
The rearrangement of analogous bromo derivatives
16‒18 was considerably faster, and the corresponding
Markovnikov adducts 4‒6 were formed even in 30 min
(in this case, the addition of chloroform was not
necessary). The higher rate of the rearrangement of
bis(1-bromoalkan-2-yl) selenides to bis(2-bromo-
alkyl) selenides in comparison to chloro-substituted
analogs was observed by us previously [13]. Presum-
ably, the rearrangement involves λ4-seleniranium
intermediates (Scheme 2) like those proposed in the
reactions of selenium tetrachloride with (Z)- and
(E)-but-2-enes, which were responsible for the stereo-
selective anti-addition [16].
λ4-Selanes 1‒6 formed in the reactions of alkenes
with SeO2‒HX (SeO2–alkene ratio 1:2) can be sepa-
rated from the corresponding selenides 7‒12 by repre-
cipitation or recrystallization from hexane or carbon
tetrachloride; however, in this case a part of the prod-
uct is lost. It is advisable to convert selenides 7‒12 to 1–
6 by halogenation of the product mixture (Scheme 3).
For this purpose, halogenating agent (sulfuryl chloride
or bromine) should be added in an amount correspond-
ing to the content of 7‒12 in the product mixture. The
yield of 1‒6 in two stages was 85‒93% calculated on
SeO2. Selanes 1‒6 can readily be reduced to selenides
7‒12 (Scheme 3). By treatment of mixtures of 1‒6 and
Increase of the amount of selenium dioxide relative
to the stoichiometric SeO2‒alkene ratio (1:2) resulted
in increase of the yield of 1‒6 and proportional
decrease of the yield of 7‒12 (calculated on the initial
alkene). When the SeO2‒alkene ratio was 5:8, the
fraction of selenides 7‒12 was reduced to 1‒3%, and
almost pure λ4-selanes 1‒3 (yield 84–88%) and 4‒6
(90–93%) were obtained.
The reactions with HBr were faster (30 min),
whereas approximately 7 h was required to attain high
yields in the reactions with HCl. In the reactions of
alkenes with SeO2‒HCl unsymmetrical dichloro-
(1-chloroalkan-2-yl)(2-chloroalkyl)-λ4-selanes 13‒15
were formed; after 30 min, their content in mixtures
with selanes 1‒3 was about 35‒45% (Scheme 2).
1
Compounds 13‒15 were characterized by H and
13C NMR spectra. They were converted to 1–3 in
a hour at room temperature in chloroform. This trans-
formation is useful for the preparation of pure selanes
1‒3. If after 7 h the reaction mixture contained some
amount of 13‒15, the mixture was dissolved in chloro-
form and stirred for 1 h. Presumably, compounds 13‒
Scheme 3.
Na2S2O5
H2O–PhH
SO2Cl2 or Br2
CCl4
R
R
R
R
Se
Se
7–12
+
1–6
X
X
X
X
X
X
1–6
7–12
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 12 2017

SYNTHESIS OF (2-HALOALKYL) SELANES AND SELENIDES
1811
Scheme 4.
Ph
Ph
Ph
Ph
Et2O–H2O
X = Br
Et2O–H2O
Br
Se
Cl
SeX4
+
2
+
Ph
CH2
X = Cl
Cl Cl
Br
Cl
Cl
Cl
19
7‒12 with an aqueous solution of sodium metabisulfite
we obtained pure selenides 7‒12 in 80‒86% yield
(calculated on the initial SeO2).
EXPERIMENTAL
The NMR spectra were recorded on a Bruker DPX-
400 spectrometer at 400.13 (1H), 100.61 (13C), and
76.30 MHz (77Se) using CDCl3 as solvent; the chemi-
cal shifts were measured relative to hexamethyldisilox-
ane (1H, 13C) and Me2Se (77Se). The solvents used
were preliminarily dried and distilled. The elemental
analyses were obtained on a Thermo Flash EA1112
analyzer.
Dihalobis(2-haloalkyl)-λ4-selanes 1‒6 (general
procedure). a. A solution of 8 mmol of terminal alkene
in 15 mL of diethyl ether was cooled to 0°C and added
to a solution of 0.555 g (5 mmol) of SeO2 in 5 mL of
36% aqueous HCl (or 46% aqueous HBr), and the
mixture was vigorously stirred for 7 h (0.5 h in the
reaction with HBr) at room temperature. The organic
layer was separated, and the aqueous layer was ex-
tracted with 10 mL of diethyl ether. The organic phase
was dried over CaCl2, and the solvent was distilled off.
For the synthesis of chloro derivatives 1‒3, the residue
was dissolved in 15 mL of chloroform, the solution
was stirred for 1 h (to convert compounds 13‒15 to
1‒3), the solvent was distilled off, and the residue
was dried under reduced pressure. Yield of 1‒3
84‒88%, and of 4‒6, 90‒93% (calculated on the initial
terminal alkene).
Styrene reacted with SeO2‒HBr to give (1,2-di-
bromoethyl)benzene in ~90% yield, while its reaction
with SeO2‒HCl afforded dichlorobis(2-chloro-2-
phenylethyl)-λ4-selane (19) as the major product (yield
72%) and (1,2-dichloroethyl)benzene as minor one
(20%) (Scheme 4). Analogous selenium(II) deriva-
tives, bis(2-chloro-2-phenylethyl) and bis(2-bromo-2-
phenylethyl) selenides, were formed in the reaction of
selenium dihalides with styrene [15]. These com-
pounds were characterized by 1H and 13C NMR spectra
but were not isolated since they slowly decomposed at
room temperature.
The structure of compounds 1‒12 and 19 was
1
13
confirmed by H and C NMR spectra and elemental
analyses. Unsymmetrical λ4-selanes 13‒15 were iden-
tified by 1H and 13C NMR in mixtures with compounds
1‒3. The isolated compounds were mixtures of two
diastereoisomers (dl and meso) at a ratio of ~1:1. The
SeCH2 and CHX carbon signals in the 13C NMR
spectra of 1‒15, as well as the selenium signals in their
77Se NMR spectra, were doubled due to the presence
of two diastereoisomers. The C–Se coupling constant
of the CH2 carbon nuclei in the 13C NMR spectra
was 59‒70 Hz, which corresponds to direct coupling
(1JC–Se) and indicates formation of Markovnikov
adducts. The selenium signals of chloroalkyl (8, 9)
and bromoalkyl selenides (11, 12) were located at
δSe 163‒169 and 199‒204 ppm, respectively, and
the selenium nucleus in λ4-selanes resonated in
a downfield region (2, 3: δSe 523‒528 ppm, Cl2SeCH2;
(5, 6: δSe 495‒499 ppm).
b. The reactions of SeO2‒HCl (HBr) with alkenes
at a SeO2‒alkene ratio of 1 :2 were carried out in
a similar way. The resulting mixtures of 1‒6 (yield 80‒
90%) and 7‒12 (5‒12%) were then subjected to
halogenation and reduction. The reaction of styrene
with SeO2‒HCl gave 72% of dichlorobis(2-chloro-2-
phenylethyl)-λ4-selane (19) and 20% of (1,2-dichloro-
ethyl)benzene.
Thus, we have developed efficient methods for the
synthesis of intermediate products for organoelement
chemistry on the basis of reactions of selenium tetra-
halides with terminal alkenes and styrene. The proce-
dure for the synthesis of selenides 7‒12 via reduction
of selanes 1‒6 seems less convenient than the one-step
synthesis of bis(2-haloalkyl) selenides via addition of
selenium dihalides to alkenes [13, 14]; however, it is
also sufficiently effective, and it can be regarded as
an alternative method with the use of SeO2.
c. A mixture of selane 1‒6 and selenide 7‒12
obtained in the reaction of alkenes with SeO2‒HCl
(HBr) was dissolved in 20 mL of carbon tetrachloride,
the solution was cooled to 0°C, and a cold (0°C)
solution of sulfuryl chloride (or bromine) in 10 mL of
carbon tetrachloride was added (the amount of the
halogenating agent corresponded to the content of
7–12 in the mixture). The mixture was stirred for 1 h at
0°C, the cooling bath was removed, and the mixture
was stirred for 1 h to allow it to warm up to room
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 12 2017

MUSALOV et al.
1812
temperature. The solvent was distilled off, and the
residue was dried under reduced pressure.
1.86–1.98 m (4H, CH2), 4.24–4.39 m (4H, CH2Se),
4.85–4.96 m (2H, CHBr). 13C NMR spectrum, δC,
ppm: 14.07 (CH3), 22.45 (CH2), 27.30 (CH2), 30.88
(CH2), 38.05 (CH2), 48.52 (CHBr), 66.31 (CH2Se),
Dichlorobis(2-chlorohexyl)-λ4-selane (1). Yield
1
88%, colorless crystals, mp 43–45°C. H NMR spec-
77
66.35 (CH2Se). Se NMR spectrum, δSe, ppm: 495.6,
trum, δ, ppm: 0.94 t (6H, CH3), 1.48–1.56 m (8H,
CH2), 2.12–2.20 m (2H, CH2), 2.24–2.32 m (2H, CH2),
4.12–4.24 m (4H, CHSe), 4.64–4.72 m (2H, CHCl).
13C NMR spectrum, δC, ppm: 14.12 (CH3), 21.92
(CH2), 30.56 (CH2), 37.35 (CH2), 56.76 (CHCl), 68.65
(CH2Se), 68.72 (CH2Se). Found, %: C 37.29; H 6.40;
Cl 36.23; Se 19.98. C12H24Cl4Se. Calculated, %:
C 37.04; H 6.22; Cl 36.45; Se 20.29.
497.7. Found, %: C 27.98; H 4.56; Br 54.09; Se 13.51.
C14H28Br4Se. Calculated, %: C 28.26; H 4.74;
Br 53.72; Se 13.27.
Dibromobis(2-bromooctyl)-λ4-selane (6). Yield
1
90%, yellowish crystals, mp 69–71°C. H NMR spec-
trum, δ, ppm: 0.79 m (6H, CH3), 1.13–1.26 m (12H,
CH2), 1.38–1.47 m (2H, CH2), 1.55–1.64 m (2H, CH2),
1.81–1.90 m (4H, CH2), 4.11–4.21 m (4H, CH2Se),
4.73–4.80 m (2H, CHBr). 13C NMR spectrum, δC,
ppm: 14.45 (CH3), 22.84 (CH2), 27.79 (CH2), 28.64
(CH2), 31.83 (CH2), 38.09 (CH2), 47.93 (CHBr), 66.82
Dichlorobis(2-chloroheptyl)-λ4-selane (2). Yield
1
87%, colorless crystals, mp 65–67°C. H NMR spec-
trum, δ, ppm: 0.90 t (6H, CH3), 1.23–1.40 m (8H,
CH2), 1.44–1.66 m (4H, CH2), 1.81–2.95 m (4H, CH2),
4.11–4.31 m (4H, CH2Se), 4.75–4.82 m (2H, CHCl).
13C NMR spectrum, δC, ppm: 13.97 (CH3), 22.42
(CH2), 26.02 (CH2), 31.02 (CH2), 37.59 (CH2), 56.74
(CHCl), 68.77 and (CH2Se), 68.88 (CH2Se). 77Se NMR
spectrum, δSe, ppm: 523.1, 525.2. Found, %: C 40.12;
H 6.62; Cl 34.27; Se 18.68. C14H28Cl4Se. Calculated,
%: C 40.31; H 6.77; Cl 34.00; Se 18.93.
77
(CH2Se). Se NMR spectrum, δSe, ppm: 497.1, 498.8.
Found, %: C 31.09; H 5.29; Br 51.53; Se 12.46.
C16H32Br4Se. Calculated, %: C 30.85; H 5.18;
Br 51.30; Se 12.67.
Bis(2-haloalkyl)selenides 7‒12 (general proce-
dure). A mixture of selane 1‒6 and selenide 7‒12
obtained in the reaction of alkenes with SeO2‒HCl
(HBr) was dissolved in 20 mL benzene, the solution
was cooled to 5°C, and a cold (5°C) solution of 3 g of
sodium metabisulfite in 20 mL of water was added.
The mixture was stirred for 1 h at 5°C, the cooling
bath was removed, and the mixture was stirred for 1 h
to allow it to warm up to room temperature. The
organic layer was separated, and the aqueous layer was
extracted with 10 mL of benzene. The organic phase
was dried over CaCl2, the solvent was distilled off, and
the residue was dried under reduced pressure.
Dichlorobis(2-chlorooctyl)-λ4-selane (3). Yield
1
84%, colorless crystals, mp 67–69°C. H NMR spec-
trum, δ, ppm: 0.80 t (6H, CH3), 1.16–1.27 m (12H,
CH2), 1.33–1.45 m (4H, CH2), 1.46–1.54 m (2H, CH2),
1.73–1.84 m (2H, CH2), 4.07–4.18 m (4H, CH2Se),
4.62–4.70 m (2H, CHCl). 13C NMR spectrum, δC,
ppm: 14.24 (CH3), 22.62 (CH2), 26.37 (CH2), 28.66
(CH2), 31.66 (CH2), 37.69 (CH2), 56.84 (CHCl), 68.78
1
1
(CH2Se, JC–Se = 60 Hz), 68.85 (CH2Se, JC–Se
=
59 Hz). 77Se NMR spectrum, δSe, ppm: 526.3, 528.3.
Found, %: C 42.94; H 7.42; Cl 32.12; Se 18.04.
C16H32Cl4Se. Calculated, %: C 43.17; H 7.24;
Cl 31.85; Se 17.74.
Bis(2-chlorohexyl) selenide (7). Yield 83%,
1
colorless oil. H NMR spectrum, δ, ppm: 0.95 t (6H,
CH3), 1.30–1.41 m (4H, CH2), 1.48–1.59 m (4H, CH2),
1.58–1.67 m (2H, CH2), 1.91–1.99 m (2H, CH2), 2.90–
2.99 m (4H, CH2Se), 3.94–4.03 m (2H, CHCl).
13C NMR spectrum, δC, ppm: 13.91 (CH3), 21.85
Dibromobis(2-bromohexyl)-λ4-selane (4). Yield
1
93%, yellowish crystals, mp 61–63°C. H NMR spec-
1
trum, δ, ppm: 0.95 t (6H, CH3), 1.46–1.54 m (8H,
CH2), 1.96–2.03 m (2H, CH2), 2.06–2.13 m (2H, CH2),
4.08–4.20 m (4H, CHSe), 4.57–4.66 m (2H, CHBr).
13C NMR spectrum, δC, ppm: 13.91 (CH3), 18.98
(CH2), 30.83 (CH2), 36.89 (CH2), 48.02 (CHBr), 66.72
(CH2Se). Found, %: C 25.17; H 4.09; Br 56.06;
Se 14.27. C12H24Br4Se. Calculated, %: C 25.42;
H 4.27; Br 56.38; Se 13.93.
(CH2), 29.06 (CH2), 33.18 (CH2Se, JC–Se = 68 Hz),
1
33.34 (CH2Se, JC–Se = 68 Hz), 37.01 (CH2), 61.72
(CHCl), 61.81 (CHCl). Found, %: C 45.57; H 7.42;
Cl 22.56; Se 25.07. C12H24Cl2Se. Calculated, %:
C 45.30; H 7.60; Cl 22.28; Se 24.82.
Bis(2-chloroheptyl) selenide (8). Yield 82%, color-
1
less oil. H NMR spectrum, δ, ppm: 0.92 t (6H, CH3),
1.29–1.42 m (10H, CH2), 1.50–1.60 m (2H, CH2),
1.61–1.70 m (2H, CH2), 1.89–1.99 m (2H, CH2), 2.87–
2.90 m (2H, CH2Se), 2.98–3.07 m (2H, CH2Se), 3.94–
4.03 m (2H, CHCl). 13C NMR spectrum, δC, ppm:
13.99 (CH3), 22.41 (CH2), 25.82 (CH2), 31.13 (CH2),
Dibromobis(2-bromoheptyl)-λ4-selane (5). Yield
1
92%, yellowish crystals, mp 64–67°C. H NMR spec-
trum, δ, ppm: 0.88 t (6H, CH3), 1.32–1.42 m (8H,
CH2), 1.43–1.53 m (2H, CH2), 1.57–1.67 m (2H, CH2),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 53 No. 12 2017

SYNTHESIS OF (2-HALOALKYL) SELANES AND SELENIDES
1813
1
1
33.25 (CH2Se, JC–Se = 69 Hz), 33.40 (CH2Se, JC–Se
=
77Se NMR spectrum, δSe, ppm: 202.0, 203.7. Found,
%: C 41.23; H 7.15; Br 34.78; Se 16.87. C16H32Br2Se.
Calculated, %: C 41.49; H 6.96; Br 34.50; Se 17.05.
69 Hz), 37.13 (CH2), 61.75 (CHCl), 61.84 (CHCl).
77Se NMR spectrum, δSe, ppm: 163.7, 164.8. Found,
%: C 48.83; H 8.34; Cl 20.23; Se 23.12. C14H28Cl2Se.
Calculated, %: C 48.56; H 8.15; Cl 20.48; Se 22.81.
Dichloro(1-chlorohexan-2-yl)(2-chlorohexyl)-λ4-
1
selane (13). H NMR spectrum, δ, ppm: 0.87–0.93 m
Bis(2-chlorooctyl) selenide (9). Yield 80%, color-
less oil. H NMR spectrum, δ, ppm: 0.77 t (6H, CH3),
(6H, CH3), 1.30–1.54 m (6H, CH2), 1.82–1.87 m (4H,
CH2), 2.11–2.18 m (2H, CH2), 4.05–4.12 m (2H,
CH2Cl), 4.18–4.27 m (2H, CH2Se), 4.51–4.58 m (1H,
1
1.12–1.26 m (14H, CH2), 1.34–1.43 m (2H, CH2),
1.45–1.54 m (2H, CH2), 1.72–1.80 m (2H, CH2), 2.77–
2.84 m (2H, CH2Se), 2.87–2.93 m (2H, CH2Se), 3.87–
3.94 m (2H, CHCl). 13C NMR spectrum, δC, ppm:
14.13 (CH3), 22.54 (CH2), 26.27 (CH2), 28.59 (CH2),
13
CHSe), 4.73–4.77 m (1H, CHCl). C NMR spectrum,
δC, ppm: 14.18 (CH3), 22.20, 22.74, 28.54, 29.30,
29.98, 37.50 (CH2), 43.82, 44.02 (CH2Cl), 57.21,
57.31 (CHCl), 65.55, 65.99 (SeCH2), 76.39, 76.98
(SeCH).
1
31.58 (CH2), 33.38 (CH2Se, JC–Se = 66 Hz), 33.52
1
(CH2Se, JC–Se = 66 Hz), 37.37 (CH2), 61.78, 61.87
Dichloro(1-chloroheptan-2-yl)(2-chloroheptyl)-
(CHCl). 77Se NMR spectrum, δSe, ppm: 167.6, 168.8.
Found, %: C 51.08; H 8.43; Cl 19.23; Se 21.42.
C16H32Cl2Se. Calculated, %: C 51.34; H 8.62;
Cl 18.94; Se 21.10.
1
λ4-selane (14). H NMR spectrum, δ, ppm: 0.90–
0.95 m (6H, CH3), 1.30–1.46 m (6H, CH2), 1.48–
1.86 m (8H, CH2), 2.17–2.22 m (2H, CH2), 4.04–
4.12 m (2H, CH2Cl), 4.15–4.25 m (2H, CH2Se), 4.46–
4.51 m (1H, CHSe), 4.72–4.77 m (1H, CHCl).
13C NMR spectrum, δC, ppm: 14.19 (CH3), 22.57,
22.67, 26.05, 26.82, 30.35, 31.16, 31.63, 37.59 (CH2),
43.42, 43.60 (CH2Cl), 56.68, 56.76 (CHCl), 65.51,
66.06 (CH2Se), 76.50, 76.96 (CHSe).
Bis(2-bromohexyl) selenide (10). Yield 86%, light
yellow oil. H NMR spectrum, δ, ppm: 0.95 t (6H,
CH3), 1.39–1.56 m (8H, CH2), 1.76 m (2H, CH2),
2.03 m (2H, CH2), 3.02–3.10 m (2H, CH2Se), 3.17–
3.22 m (2H, CH2Se), 4.09 m (2H, CHBr). 13C NMR
spectrum, δC, ppm: 13.91 (CH3), 21.89 (CH2), 29.29
1
Dichloro(1-chlorooctan-2-yl)(2-chlorooctyl)-λ4-
1
(CH2), 33.71 (SeCH2, JC–Se = 69 Hz), 33.95 (SeCH2,
1
1JC–Se = 69 Hz), 37.04 (CH2), 54.25 (CHBr), 54.44
(CHBr). Found, %: C 35.67; H 6.09; Br 38.93;
Se 19.18. C12H24Br2Se. Calculated, %: C 35.40;
H 5.94; Br 39.26; Se 19.40.
selane (15). H NMR spectrum, δ, ppm: 0.90–0.96 m
(6H, CH3), 1.32–1.44 m (10H, CH2), 1.54–1.70 m (6H,
CH2), 1.92–1.98 m (2H, CH2), 2.21–2.30 m (2H, CH2),
4.03–4.13 m (2H, CH2Cl), 4.16–4.28 m (2H, CH2Se),
4.48–4.54 m (1H, CHSe), 4.78–4.82 m (1H, CHCl).
13C NMR spectrum, δC, ppm: 14.27 (CH3), 22.64,
22.66, 26.33, 27.14, 28.67, 29.20, 30.43, 31.56, 31.70,
37.65 (CH2), 43.42, 43.60 (CH2Cl), 56.68, 56.76
(CHCl), 65.51, 66.06 (SeCH2), 76.50, 76.96 (CHSe).
Bis(2-bromoheptyl) selenide (11). Yield 85%, light
yellow oil. H NMR spectrum, δ, ppm: 0.92 t (6H,
CH3), 1.35 m (10H, CH2), 1.58 m (2H, CH2), 1.75 m
(2H, CH2), 2.01 m (2H, CH2), 3.06 m (2H, CH2Se),
3.21 m (2H, CH2Se), 4.09 m (2H, CHBr). 13C NMR
spectrum, δC, ppm: 13.89 (CH3), 22.29 (CH2), 26.76
1
Bis(2-chloro-2-phenylethyl)-λ4-selane (19). Yield
1
1
(CH2), 30.89 (CH2), 33.68 (CH2Se, JC–Se = 70 Hz),
72%, colorless crystals, mp 91–93°C. H NMR spec-
1
33.90 (CH2Se, JC–Se = 70 Hz), 37.30 (CH2), 54.30
trum, δ, ppm: 3.88–3.97 m (2H, SeCH2), 4.06–4.15 m
(2H, SeCH2), 5.38–5.47 m (2H, ClCH), 6.93–7.01 m
(6H, Ph), 7.04–7.10 m (4H, Ph). 13C NMR spectrum,
δC, ppm: 57.18 (CHCl), 68.90, 69.00 (SeCH2), 127.40,
129.23, 129.93, 136.81 (Ph). Found, %: C 45.02;
H 3.93; Cl 32.79; Se 18.67. C16H16Cl4Se. Calculated,
%: C 44.79; H 3.76; Cl 33.05; Se 18.40.
(CHBr), 54.48 (CHBr). 77Se NMR spectrum, δSe, ppm:
199.4, 201.1. Found, %: C 38.37; H 6.31; Br 36.59;
Se 18.39. C14H28Br2Se. Calculated, %: C 38.64;
H 6.49; Br 36.73; Se 18.15.
Bis(2-bromooctyl) selenide (12). Yield 84%, light
yellow oil. H NMR spectrum, δ, ppm: 0.86 t (6H,
1
CH3), 1.22–1.34 m (6H, CH2), 1.36–1.42 m (2H, CH2),
1.48–1.56 m (2H, CH2), 1.69–1.78 m (2H, CH2), 1.95–
2.03 m (2H, CH2), 3.02–3.11 m (2H, CH2Se), 3.18–
3.23 m (2H, CH2Se), 4.10–4.18 m (2H, CHBr).
13C NMR spectrum, δC, ppm: 14.09 (CH3), 22.58
(CH2), 27.34 (CH2), 28.55 (CH2), 31.62 (CH2), 33.92
The spectral studies were carried out using the
facilities of the Baikal Joint Analytical Center, Siberian
Branch, Russian Academy of Sciences.
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1
(CH2Se, JC–Se = 69 Hz), 34.19 (CH2Se, JC–Se
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