Regioselective addition of sulfur dichloride and selenium tetrachloride to diallyldimethylsilane as the method of preparation of eight-membered heterocycles containing silicon and chalcogens

Article abstract of DOI:10.1134/S1070428010110114

The electrophilic additiob of sulfur dichloride and selenium tetrachloride to diallyldimethylsilane proceeds strictly according Markownikoff rule and results in the formation of previously unknown saturated silicon-containing heterocycles, 5,5-dimethyl-3,7-dichloro-1,5-thiasilacyclooctane and 5,5-dimethyl-1,1,3,7-tetrachloro-1,5-selena(IV)silacyclooctane. The structure of heterocycles obtained was confi rmed by ¹H, ¹³C NMR spectra, in the case of selenium-containing heterocycle, by ⁷⁷Se NMR spectrum, among them the 2D HMBC spectrum. Pleiades Publishing, Ltd., 2010.

Full text of DOI:10.1134/S1070428010110114

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2010, Vol. 46, No. 11, pp. 1675−1677. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © A.V. Martynov, N.A. Makhaeva, L.I. Larina, S.V. Amosova, 2010, published in Zhurnal Organicheskoi Khimii, 2010, Vol. 46, No. 11,
pp. 1668−1670.
Regioselective Addition of Sulfur Dichloride
and Selenium Tetrachloride to Diallyldimethylsilane
as the Method of Preparation of Eight-Membered
Heterocycles Сontaining Silicon and Chalcogens
A. V. Martynov, N. A. Makhaeva, L. I. Larina, and S. V. Amosova
Faworsky Irkutsk Institute of Chemistry, Siberian Division, Russian Academy of Sciences, Irkutsk, 664033 Russia
e-mail: martynov@irioch.irk.ru
Received March 4, 2010
Abstract—The electrophilic additiob of sulfur dichloride and selenium tetrachloride to diallyldimethylsilane
proceeds strictly according Markownikoff rule and results in the formation of previously unknown saturated silicon-
containing heterocycles, 5,5-dimethyl-3,7-dichloro-1,5-thiasilacyclooctane and 5,5-dimethyl-1,1,3,7-tetrachloro-
,5-selena(IV)silacyclooctane. The structure of heterocycles obtained was confirmed by H, 13C NMR spectra,
1
1
in the case of selenium-containing heterocycle, by 77Se NMR spectrum, among them the 2D HMBC spectrum.
DOI: 10.1134/S1070428010110114
The electrophilic addition of sulfur dichloride to
diallyl systems like 1,5-hexadiene, diallyl sulfide and
ether proceeds in pentane at 0°C as anti-Markownikoff
addition at both allyl fragments with the formation of the
corresponding five- and six-membered saturated hetero-
cycles [1]. Analogously as anti-Markownikoff addition
to the double bond of the allyl fragment the electrophilic
reaction of sulfur dichloride occurs with diallyl ethers of
glycols and mercaptophenols, allyl ethers of phenols and
allyl aryl sulfides, resulting in sulfur-containing macro-
cyclic oxathia- and thiacrown ethers [2]. However with
allylbenzenes the regioselectivity is opposite, and with
a 100% selectivity only the products of Markownikoff
addition are formed [2].
to the Markownikoff rule and resulted in the formation
of previously unknown saturated eight-membered hetero-
cycles containing chalcogens and silicon, 5,5-dimethyl-
3,7-dichloro-1,5-thiasilacyclooctane (I) in the case of
SCl and 5,5-dimethyl-1,1,3,7-tetrachloro-1,5-selena(IV)
2
silacyclooctane (II) in the case of SeCl (Scheme 1) in
4
77 and 98% yield, respectively.
The structure of obtained heterocycles was confirmed
1
13
29
77
1
by the data of H, C, Si, Se NMR spectra. H NMR
spectra of the heterocycles contain a multiplet signal of
groups CHCl, two multiplet signals of nonequivalent
Scheme 1.
Me
Me
The electrophilic addition of selenium monochloride
Se Cl to 1,5-hexadiene and diallyl ether also proceeds
SCl2
Si
2
2
against the Markownikoff rule and is accompanied with
the elimination of one selenium atom. As a result with
_
Cl
Cl
hexane, 20°C
Cl
Cl
Me
Me
S
1,5-hexadiene formed a five-membered saturated hetero-
Si
I
cycle, with diallyl ether, six-membered heterocycle. In
both cases formed a single isomer that was assigned a cis-
configuration as more feasible thermodynamically [3].
Me
Me
Si
SeCl4
We established that unlike the known reactions of
the diallyl systems the reactions of sulfur dichloride
and selenium tetrachloride with diallyldimethylsilane at
_
CHCl , 40°C
3
Se
Cl
Cl
–20...–40°C in hexane or chloroform proceeded according
II
1
675

1676
MARTYNOV et al.
protons of groups CH Y (Y = S, SeCl ), two multiplet
(III) (Scheme 2) thus confirming the assumed structure of
heterocycle I. Sulfide III was identified by the H NMR
2
2
1
signals of protons of groups CH Si, and singlet signals
2
of the Me Si group. The presence of strong electron-
spectrum identical to that of the standard sample. In the
GC-MS spectrum of the reaction mixture the correspond-
ing molecular ion was observed.
2
withdrawing chlorine atoms in the SeCl group of het-
2
erocycle II results in a sharp downfield shift of the proton
signals of CHCl groups (by 0.8 ppm) and CH SeCl
2
2
The formation of the diallyl sulfide may be ascribed
to the ready desilylation of the relatively weak C–Si bond
of the intermediately formed carbocation containing in
the vicinal position a silyl group. The C–Si bond is even
more destabilized due to the hyperconjugation with the
positive charge [6] (the so-called β-effect [7–9]).
groups (by 1.3 ppm) as compared to the signals of analo-
1
3
gous protons in heterocycle I. The C NMR spectra of
heterocycles I and II contain doublet signals of carbon
atoms from CHCl groups, triplet signals from CH Y
2
(
Y = S, SeCl ) and CH Si groups, and a quartet from the
2 2
dimethylsilyl group. The presence in the molecules of
compounds I and II of CHCl and CH Y (Y = S, SeCl )
2
2
EXPERIMENTAL
groups is shown first of all by the characteristic values
of the corresponding coupling constants 1JCH of carbon
atoms, indicating the direct bonding of the carbon atom
with a chlorine in the first case and with a chalcogen in
the second [4]. The presence in the heterocycle II of the
1
13
29
H(400.13MHz), C(100.61MHz), Si(79.50MHz),
77Se (76.31 MHz) NMR spectra were registered on spec-
trometers Bruker DPX-400 and AV-400 frpm 5–10%
solutions in CDCl . For heterocycle II a 77Se NMR
3
7
7
SeCl group is seen from the Se NMR spectrum where
2
spectrum was obtained by the use of 2D NMR, method
two multiplet selenium signals (δ 533.6 and 531.8 ppm)
1
77
HMBC GP H- Se. GC-MS spectrum was obtained on an
instrument Shimadzu QP5050Aat the energy of ionizing
electrons 70 eV, capillary colun SPB-5, 60 m × 0.25 mm,
.25 μm, vaporizer temperature 260°C, oven temperature
50–220°C. Diallyldimethylsilane was synthesized from
-chloropropene and trimethylchlorosilane by Grignard
reaction [10]. SCl was prepared by chlorination of S Cl
appear in the range characteristic of compounds RSeCl R
2
7
7
[
5]. The presence of two signals of Se atoms shows that
heterocycle II forms as two diastereomers owing to anti,
anti- and anti,syn-addition of SeCl to allyl fragments. It
0
4
1
3
is also proved by the presence in the C NMR spectrum
of two signals from the (CH ) SeCl2. The Markownikoff
structure of heterocycle II was confirmed by the 2D H-
Se NMR spectrum HMBC where cross-peaks of atom
Se with protons of CH groups at 4.20–4.33 ppm were
3
2
2
2
2
2
1
[
11].
,5-Dimethyl-3,7-dichloro-1,5-thiasilacycloctane
I). To a solution of 2.13 g (15.2 mmol) of diallyldi-
7
7
5
7
7
2
(
observed.
In the 29Si NMR spectra of heterocycles the silicon
signal appears in the region 1.7–2.8 ppm.
,1,3,7-Tetrachloro-1,5-selenasilacyclooctane (II)
methylsilane in 60 ml of hexane at –20°C within 25 min
was added a solution of 1.56 g (15.2 mmol) of SCl in
5 ml of hexane. The reaction mixture was stirred for
3 h gradually warming it to room temperature, and it
was left overnight. The reaction mixture separated in two
colorless layers. The upper hexane layer was decanted,
the bottom layer was treated with chloroform. After
removal of solvent from the extract we obtained 2.12 g
of heterocycle I as a colorless viscous fluid. The residue
after removal of the solvent from the hexane solution
2
1
1
formed as yellowish fine-crystalline powder at storage at
the room temperature within 24 h hydrolizes and decom-
poses, but at –20°C it can be stored for several weeks.
The heating of heterocycle I and also its treatment with
dehydrochlorinating reagents (t-BuOK in t-BuOH, Et N,
3
DBU) leads to the dechlorination–desilylation with the
cleavage of the ring and the formation of diallyl sulfide
1
weighed 1.50 g and contained according the H NMR
Scheme 2.
t-BuOK/t-BuOH,
Me Me
Si
Me
Me
Me
Me
_
or Et N,
3
Cl
Si Cl
_
Si Cl
or DBU
Cl
I
+
S
III
Cl
+
Cl
S
S
S
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 11 2010

REGIOSELECTIVE ADDITION OF SULFUR DICHLORIDE
1677
1
29
data 47% of heterocycle I together with the products
of its decomposition, including diallyl sulfide (III).
Overall yield of heterocycle I 77%. H NMR spectrum,
(CH SeCl , J 147.6 Hz). Si NMR spectrum, δ, ppm:
2
2
CH
77
2.8. Se NMR spectrum, δ, ppm: 533.6 m, 531.8 m (1:1).
Found, %: C 25.90; H 4.52; Cl 39.01; Se 21.60; Si 7.44.
C H Cl SeSi. Calculated, %: C 26.61; H 4.47; Cl 39.28;
1
δ, ppm: 0.20 s [6H, (CH ) Si], 1.27–1.25 m, 1.49–1.46
3
2
8
16
4
m [4H, (CH ) Si], 2.91–2.89 m, 3.00 m [4H, (CH ) S],
Se 21.87; Si 7.78.
2
2
2 2
1
3
4
.17 m (2H, 2CHCl). C NMR spectrum, δ, ppm: –1.70
1
1
q [(CH ) Si, J 119.5 Hz], –1.50 q [(CH ) Si, J
3
2
CH
3 2
CH
ACKNOWLEDGMENTS
1
1
18.3 Hz], 25.65 t (CH Si, J 118.1 Hz), 45.09 t (CH S,
2 CH 2
1JCH 142.3 Hz), 60.27 d (2CHCl, 1JCH 155.9 Hz). 29Si
The study was carried out under the financial support
of the Presidium of the Russian Academy of Sciences
(grant 18.19) and of the Russian Foundation for Basic
Research (grant 10-03-00-543a).
NMR spectrum, δ, ppm: 1.7. Found, %: C 38.97; H 6.50;
Cl 28.60; S 13.68; Si 11.37. C H Cl SSi. Calculated, %:
8
16
2
C 39.50; H 6.63; Cl 29.15; S 13.18; Si 11.55.
To 0.208 g (0.85 mmol) of heterocycle I was added
.260 g (1.71 mmol) of DBU in 8 ml of Et O, and the
2
REFERENCES
0
mixture was stirred for 6 h. Then the reaction mixture was
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1
2
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+
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2
2
5
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1
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4
2
2
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3
3
under argon was quickly added 0.392 g (2.79 mmol)
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3
was stirred at the same temperature for 1.5 h, then it
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8
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9
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crystalline powder, mp 59–60°C (hexane). H NMR
1
1
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2
1
[
.50–1.57 m [4H, (CH ) Si], 4.20 m, 4.28–4.33 m
2 2
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2
2
2
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1
spectrum, δ, ppm: –1.79 q [(CH ) Si, J 119.3 Hz],
2
1
3
2
CH
1
1
6.09 t (CH Si, J 117.6 Hz), 54.79 d (2CHCl, J
2 CH CH
1
57.1 Hz), 70.75 t (CH SeCl , J 150.4 Hz), 70.91 t
2
2
CH
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 46 No. 11 2010