Unexpected reaction of alkyl 2,2-dichlorovinyl sulfones with sodium selenide

Full text of DOI:10.1134/S1070428013060237

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2013, Vol. 49, No. 6, pp. 930–932. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © A.V. Martynov, N.S. Monareva, L.I. Larina, S.V. Amosova, 2013, published in Zhurnal Organicheskoi Khimii, 2013, Vol. 49, No. 6,
pp. 943–945.
SHORT
COMMUNICATIONS
Unexpected Reaction of Alkyl 2,2-Dichlorovinyl Sulfones
with Sodium Selenide
A. V. Martynov, N. S. Monareva, L. I. Larina, 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 December 26, 2012
DOI: 10.1134/S1070428013060237
Alkyl 2,2-dichlorovinyl sulfones were reported to
react with sodium sulfide to give 2,6-bis(alkylsul-
fonyl)-1,4-dithiafulvenes [1]. Reaction of alkyl 2,2-di-
chlorovinyl sulfones with sodium selenide may also be
anticipated to produce analogous 1,4-diselenafulvenes;
however, it has not been reported. Various methods for
the generation of sodium selenide are known; among
these, the most convenient is that implying reduction
of elemental selenium with sodium tetrahydridoborate
in ethanol [2–4]. It should be kept in mind that high
basicity of sodium ethoxide generated in the above
reductive system could promote rearrangement of
pectedly afforded bis(2-alkylsulfonylethyl) diselenides
IIa and IIb in high yields (Scheme 1).
The structure of diselenides IIa and IIb was proved
1
13
77
1
by the H, C, and Se NMR data. Their H NMR
spectra contained signals from protons in the alkyl
group (C H or C H ) and multiplet signals at δ 3.21–
4
9
6
13
3.26 and 3.35–3.40 ppm corresponding to the CH Se
2
and CH SO fragments. The signals were assigned by
2
2
1
3
1
13
comparing the C NMR and two-dimensional H– C
HMBC spectra. In the C NMR spectra of IIa and IIb
13
we observed two groups of signals, upfield signals in
the region δ
signals at δ
IIa) and 18.26 ppm (IIb) showed a direct spin–spin
13.00–32.00 ppm and two downfield
C
2
,2-dichlorovinyl sulfones into more thermodynami-
C
53.00–55.00 ppm. The signals at δ 18.22
C
(
cally stable 1,2-dichlorovinyl sulfones [5]. The latter
are known in turn to undergo hydrolysis to chloro-
methyl sulfones by the action of 5% alkali [6]. There-
fore, the reaction of alkyl 2,2-dichlorovinyl sulfones
with sodium selenide may be expected to be largely
determined by the conditions of generation of the
latter.
7
7
coupling constant with Se, indicating that the corre-
sponding carbon atoms are directly linked to selenium.
The presence of cross peaks between the above carbon
signals and proton signals at δ 3.21–3.26 ppm in the
1
13
H– C HMBC spectrum allowed us to reliably assign
the former to the CH Se fragment of the
2
SeCH CH SO group. Signals from the selenium
2
2
2
While studying the reaction of alkyl 2,2-dichloro-
vinyl sulfones with sodium selenide generated in
77
atoms appeared in the Se NMR spectra as triplets
rather than quintets that might be expected for selenide
structure. The sulfonyl group in compounds IIa and
IIb gave rise to characteristic IR absorption bands at
ethanol at different Se-to-NaBH ratios, we found that
4
at a Se-to-NaBH ratio of 1:2.7 (i.e., under the con-
4
–
1
ditions reported for the synthesis of dipropargyl sele-
nide from propargyl bromide [4]) the reaction unex-
1
100 and 1300 cm .
The diselenide structure of II was also confirmed
by generation therefrom of sodium 2-sulfonylethyl-
Scheme 1.
selenolates by the action of NaBH in alcohol; the
4
NaBH , Se
4
Cl
O
O
subsequent reaction of these intermediates with allyl
bromide produced previously unknown allyl selenides
IIIa and IIIb (Scheme 2). Their structure was con-
O
O
EtOH
S
Se
R
S
R
Se
S
R
Cl
O
O
Ia, Ib
IIa, IIb
1
13
77
firmed by the H, C, and Se NMR and mass spectra.
The latter contained strong peaks from the molecular
4 9 6
R = C H (a), C H13 (b).
9
30

9
31
UNEXPECTED REACTION OF ALKYL 2,2-DICHLOROVINYL SULFONES
Scheme 2.
CH =CHCH Br
EtOH
2
2
O
O
O
O
EtOH
IIa, IIb
+
NaBH4
S
S
CH
2
R
SeNa
R
Se
IIIa, IIIb
+
+
2
1
1
and fragment ion peaks ([SeCH CH=CH ] , [RSO ] ,
125.4, J = 4 Hz), 18.22 t (CH Se, J = 147.1, JC–Se =
2
2
2
2
+
3′
1
2′ 1
[
CH CH=CH ] ). Compounds IIIa and IIIb displayed
80.5 Hz), 21.91 t (C , J = 126.7 Hz), 24.06 t (C , J =
129.0 Hz), 53.39 t.t (C , J = 136.1, J = 4.2 Hz),
54.37 t (SO
Se 355.6 ppm, t ( J = 15.3 Hz). Found, %: C 30.93;
H 5.44; S 13.50; Se 34.32. C H O S Se . Calculated,
: C 31.58; H 5.74; S 14.05; Se 34.60.
Bis(2-hexylsulfonylethyl) diselenide (IIb) was
synthesized in a similar way. Yield 80%, light orange
finely crystalline powder, mp 137°C. IR spectrum, ν,
2
2
1
13
1′
1
2
in the H and C NMR spectra signals from protons
and carbon nuclei in the alkyl group R, CH CH group,
1
77
CH , J = 140.6 Hz). Se NMR spectrum:
2
2
2
2
2
and allyl group.
δ
1
2
26
4
2
2
The formation of diselenides II in the described
reaction may be rationalized by the presence in the
reaction mixture of both NaSeH (generated by reaction
of selenium with 1 equiv of NaBH ) and excess
NaBH used to reduce selenium to Na Se and Na Se
%
4
4
2
2
2
–
1
[
2, 4]. Sodium tetrahydridoborate is likely to promote
previously unknown successive reductive dechlorina-
cm : 1320, 1302, 1181, 1136, 1126, 1110 (SO ).
H NMR spectrum, δ, ppm: 0.89 t (3H, CH ), 1.30–
3
2
1
tion of alkyl 2,2-dichlorovinyl sulfones (I) to alkyl
134 m (4H, 4′-H, 5′-H), 1.41–1.48 m (2H, 3′-H), 1.81–
1.88 m (2H, 2′-H), 2.98–3.01 m (2H, 1′-H), 3.21–
2
-chloroethyl sulfones which react with NaSeH, yield-
ing diselenides II. Sodium tetrahydridoborate is used
as reagent in the reductive hydrodechlorination of
chloroethenes [7], aryl chlorides [8], and α-halo
3.25 m (2H, CH
2
Se), 3.35–3.40 m (2H, SO
C NMR spectrum, δ , ppm: 14.08 q (CH
124.8 Hz), 18.26 t.t (CH
2
CH ).
, J =
2
1
3
1
C
3
1
2
Se, J = 147.4, J = 5.8,
2
1
2′ 1
ketones [9]. We found that NaBH in ethanol reduces
JC–Se = 72 Hz), 22.07 t (C , J = 129.6 Hz), 22.51 t
4
5
′
1
3′
1
butyl 2,2-dichlorovinyl sulfone (Ib) to butyl ethyl
sulfone (IV) (Scheme 3). This reaction proves inter-
mediate formation of alkyl 2-chloroethyl sulfones in
the process leading to diselenides II.
(C , J = 125.4 Hz), 28.34 t (C , J = 127.7 Hz),
31.40 t (C , J = 125.8 Hz), 53.70 t.t (C , J = 136.1,
4
′
1
1′ 1
2
7
1
J = 4 Hz), 54.41 t (SO
Se NMR spectrum: δSe 337.1 ppm, t ( J = 16.6 Hz).
CH
, J = 140.3 Hz).
2
2
7
2
Found, %: C 36.95; H 6.51; S 13.02; Se 30.61.
C H O S Se . Calculated, %: C 37.50; H 6.69;
S 12.51; Se 30.81.
Scheme 3.
1
6
34
4
2
2
NaBH , EtOH
NaBH , EtOH
4
4
Ia
[BuSO CH CH Cl]
BuSO Et
2
2
2
2
Allyl (2-butylsulfonylethyl) selenide (IIIa).
Sodium tetrahydridoborate, 0.232 g (6.0 mmol), was
added to a solution of 0.456 g (1.0 mmol) of diselenide
IIa in 15 ml of ethanol until the mixture turned color-
less, a solution of 0.484 g (4.0 mmol) of allyl bromide
in 3 ml of ethanol was added, and the mixture was
stirred for 2 h, diluted with water, and extracted with
IV
Bis(2-butylsulfonylethyl) diselenide (IIa). Sodium
tetrahydridoborate, 1.279 g (33.8 mmol), was added
under argon to 0.950 g (12 mmol) of finely dispersed
selenium in 10 ml of anhydrous oxygen-free ethanol
on cooling to 0°C. A solution of 2.171 g (10 mmol) of
butyl 2,2-dichlorovinyl sulfone (Ia) in 5 ml of ethanol
was added to the resulting colorless solution of
NaSeH, the mixture was stirred for 7 h at 0°C, and
water was added to dissolve the white solid separated
from the mixture. The product was extracted into
chloroform, the extract was dried over Na SO , and the
diethyl ether. The extracts were dried over MgSO , and
4
the solvent and excess allyl bromide were removed
under reduced pressure. Yield 0.500 g (93%), yellow-
1
ish tarry substance. H NMR spectrum, δ, ppm: 0.96 t
(3H, CH , J = 7.4 Hz), 1.43–1.52 m (2H, CH ), 1.76–
3
2
1.84 m (2H, CH , J = 7.4 Hz), 2.83 t (2H, 1′-H, J =
2
4
2
solvent was distilled off under reduced pressure. Yield
.690 g (74%), light orange finely crystalline powder,
8.3 Hz), 2.97 t (2H, CH Se, J = 8.0 Hz), 3.24 t (2H,
2
1
SO CH , J = 7.2 Hz), 3.25 d (2H, CH CH=, J =
2
2
2
–
1
mp 134°C. IR spectrum, ν, cm : 1320, 1301, 1180,
7.4 Hz), 5.05–5.11 m (2H, CH =), 5.82–5.91 m (1H,
2
1
13
1
138, 1125 (SO ). H NMR spectrum, δ, ppm: 0.97 t
=CH). C NMR spectrum, δ , ppm: 12.73 t.t (SeCH ,
C
2
2
1
2
1
(
3H, CH , J = 1.0 Hz), 1.44–1.54 m (2H, 3′-H), 1.80–
J = 144.3, J = 4.0 Hz), 13.49 q.m (CH , J =
3
3
1
2
1
3
.88 m (2H, 2′-H), 2.99–3.03 m (2H, 1′-H), 3.21–
125.3 Hz), 21.65 t.t.d (SeCH , J = 127.2, J = 7.3,
2
1
.25 m (2H, CH Se), 3.36–3.40 m (2H, SO CH ).
3.7 Hz), 23.81 t.m (CH , J = 128.6 Hz), 26.62 t.m
(CH , J = 137.9 Hz), 52.57 t.t (C , J = 135.8, J =
2
2
2
2
1
3
1
1
1′
1
2
C NMR spectrum, δ , ppm: 13.71 q.t (CH , J =
2
C
3
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 6 2013

MARTYNOV et al.
932
1
2
+
4
.3 Hz), 53.70 t.t (SO CH , J = 139.0, J = 3.2 Hz),
4.2 Hz). Mass spectrum, m/z (I , %): 150 (2) [M] ,
2
2
rel
1
+
1
17.17 t.m (=CH , J = 157.1 Hz), 134.21 d.t.d (=CH,
J = 157.5, J = 4.5, 2.7 Hz). Se NMR spectrum:
δ 216.6 ppm. Mass spectrum, m/z (I , %): 270 (21.4)
121 (30) [M – C H ] , 95 (72), 57 (100). Found, %:
C 47.68; H 9.51; S 21.02. C H SO . Calculated, %:
2
2
5
1
2
77
6 14 2
Se
rel
C 47.97; H 9.39; S 21.34. M 150.24.
+
+
[
(
(
M] , 229 (2.2) [M – CH CH=CH ] , 173 (6.3), 149
2 2
Butyl and hexyl 2,2-dichlorovinyl sulfones Ia and
Ib were synthesized according to the procedure de-
scribed in [11] by oxidation of the corresponding butyl
and hexyl 2,2-dichlorovinyl sulfides with hydrogen
peroxide in acetic acid. The H (400.13 MHz),
C (100.61 MHz), and Se (76.30 MHz) NMR spec-
tra were recorded on a Bruker DPX-400 spectrometer
18.2), 133 (10.9), 121 (100), 107 (8.5), 93 (29.4), 67
39.2), 57 (38). Found, %: C 39.70; H 6.32; S 11.63;
Se 28.98. C H O SSe. Calculated, %: C 40.14;
9
18
2
H 6.74; S 11.91; Se 29.32. M 269.26.
1
1
3
77
Allyl (2-hexylsulfonylethyl) selenide (IIIb) was
synthesized in a similar way from 0.156 g (0.3 mmol)
of diselenide IIb and 0.051 g (1.1 mmol) of NaBH in
5 ml of EtOH. Yield 0.160 g (90%). H NMR spec-
1
from solutions in CDCl
using tetramethylsilane ( H,
C) and Me Se ( Se) as internal references. The mass
2
4
3
1
13
77
1
trum, δ, ppm: 0.89 t (3H, CH , J = 6.7 Hz), 1.29–
spectra (electron impact, 70 eV) were obtained on
an Agilent 5975 GC–MS system. The IR spectra of
diselenides IIa and IIb were measured on a Bruker
IFS 25 spectrometer with Fourier transform.
3
1
1
.33 m (4H, CH CH ), 1.40–1.47 m (2H, CH ), 1.78–
2 2 2
.86 m (2H, CH ), 2.84 t (2H, 1′-H, J = 8.6 Hz), 2.96 t
2
(
2H, SO CH , J = 8.0 Hz), 3.25 t (2H, CH Se, J =
2 2 2
9
5
.1 Hz), 3.25 d (2H, CH CH=, J = 8.9 Hz), 5.05–
2
This study was performed under financial support
by the Russian Foundation for Basic Research (project
no. 11-03-00810).
1
3
.11 m (2H, CH =), 5.83–5.90 m (1H, =CH). C NMR
2
1
2
spectrum, δ , ppm: 12.84 t.t (CH , J = 144.4, J =
4
C
2
1
1
Hz), 13.95 q (CH , J = 124.3 Hz), 21.93 t (CH , J =
29.5 Hz), 22.31 t (CH , J = 126.4 Hz), 26.78 t (CH ,
3
2
1
1
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2
2
1
1
J = 142.3 Hz), 28.16 t (CH , J = 125.6 Hz), 31.21 t.m
2
1
1′
1
2
1
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(
CH , J = 126.0 Hz), 53.00 t.t (C , J = 136.0, J =
2
1
2
4
.4 Hz), 53.82 t.t (SO CH , J = 138.8, J = 3.3 Hz),
2 2
1
1
117.30 t (=CH , J = 157.1 Hz), 134.28 d (=CH, J =
2
7
7
2. Klayman, D.L. and Griffin, T.S., J. Am. Chem. Soc.,
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1
57.1 Hz). Se NMR spectrum: δ 216.7 ppm. Mass
Se
1
+
spectrum, m/z (I , %): 298 (17.3) [M] , 257 (2.0)
rel
+
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2 2
1
21 (100), 93 (43.8), 85 (33.0), 67 (47.0), 55 (70.7).
Found, %: C 45.02; H 7.80; S 10.78; Se 26.13.
C H O SSe. Calculated, %: C 44.74; H 7.46;
S 10.79; Se 26.56. M 297.32.
1
1
22
2
Reductive dechlorination of butyl 2,2-dichloro-
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4
. Amosova, S.V. and Martynov, A.V., Russ. J. Org.
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(
(
3.9 mmol), was added to a solution of 0.312 g
1.4 mmol) of sulfone Ia in 5 ml of EtOH. The mixture
5
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was stirred for 5 h, diluted with water, and extracted
with diethyl ether. The extracts were dried over
Na SO and evaporated. Yield of butyl ethyl sulfone
2
4
6. Brown, M.S., J. Org. Chem., 1970, vol. 35, p. 2831.
(IV) 0.050 g (24%), white finely crystalline powder,
7. Song, H. and Carraway, E.R., Appl. Catal. B, 2008,
mp 47–48°C; published data [10]: mp 49–50°C.
vol. 78, p. 53.
1
H NMR spectrum, δ, ppm: 0.96 t (3H, CH , J =
3
8
. Scrivanti, A., Vicentini, B., Beghetto, V., Chessa, G., and
Matteoli, U., Inorg. Chem. Commun., 1998, vol. 1,
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7
.5 Hz), 1.39 t (3H, CH , J = 7.5 Hz), 1.43–1.53 m
3
(
2H, CH ), 1.78–1.86 m (2H, CH ), 2.95 t (2H, 1′-H,
2
2
1
3
J = 8.6 Hz), 2.97 q (CH SO , J = 7.6 Hz). C NMR
spectrum, δ , ppm: 6.71 q.t (CH , J = 130.5, J =
2
2
9. Ono, A., Yamaguchi, R., and Shirai, Y., Z. Naturforsch.,
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1
2
C
3
1
2
3
2
1
.7 Hz), 13.64 q.t (CH , J = 125.5, J = 4.0 Hz),
3
1
1
1.86 t (CH , J = 128.9 Hz), 23.95 t.m (CH , J =
2
2
2
1
25.9, J = 4.7 Hz), 47.04 t.q (CH CH SO , J = 136.7,
3
2
2
2
1
2
J = 4.4 Hz), 51.72 t.t (CH CH SO , J = 135.7, J =
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2
2
2
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 49 No. 6 2013