Synthesis of divinylsulfides

Article abstract of DOI:10.1055/s-0029-1218625

Arylacetylenes react with sodium sulfide in the presence of water to yield divinylsulfides. The reaction proceeds in good to excellent yield for both electron-neutral and electron-deficient aromatic systems; for electron-rich aryls, longer reaction times are necessary. The sulfides represent useful substrates for further transformations, for example, oxidation to the corresponding divinylsulfoxides and divinylsulfones. Three selected divinylsulfide derivatives were oxidized selectively to the corresponding sulfoxides or sulfones. Georg Thieme Verlag Stuttgart ? New York.

Full text of DOI:10.1055/s-0029-1218625

PAPER
947
Synthesis of Divinylsulfides
D
ivinylsul
a
fides n Paradies*
Department of Organic Chemistry, University of Karlsruhe (TH), Fritz-Haber-Weg 6, 76131 Karlsruhe, Germany
Fax +49(721)6088581; E-mail: jan.paradies@ioc.uka.de
Received 19 October 2009; revised 16 November 2009
by Wittig reaction of a,a¢-diphosphonium sulfides with
aldehydes11 or by decomposition of cysteine with sodium
ethoxide in the presence of phenyl acetylene (1).12 These
procedures furnish the divinylsulfides either as cis,trans
Abstract: Arylacetylenes react with sodium sulfide in the presence
of water to yield divinylsulfides. The reaction proceeds in good to
excellent yield for both electron-neutral and electron-deficient aro-
matic systems; for electron-rich aryls, longer reaction times are nec-
essary. The sulfides represent useful substrates for further isomers or as cis,cis isomers in low yield.
transformations, for example, oxidation to the corresponding divi-
It is well known that terminal alkynes can be attacked by
nylsulfoxides and divinylsulfones. Three selected divinylsulfide de-
rivatives were oxidized selectively to the corresponding sulfoxides
or sulfones.
nucleophiles such as amines, phosphines and thiols.13 Ac-
cordingly, we found that the addition of sodium sulfide (2)
to phenyl acetylene (1) furnishes bis(2-phenylvinyl)sul-
fide. Examples of this reaction have been reported by
Trofimov.14 Here, we present a simple and practical pro-
cedure for the synthesis of bis(arylvinyl)sulfides that does
not require the use of a,a¢-dichlorosulfides or elemental
alkali metals.
Key words: alkynes, divinylsulfoxide, sulfoxide, sulfone, sodium
sulfide
Organosulfur compounds contain highly diverse function-
al groups that allow further transformations and, more
importantly, asymmetric synthesis.1 In particular, the sul-
foxides and sulfones have attracted significant interest
from organic chemists. The sulfoxides allow a wide array
of auxiliary controlled asymmetric synthesis to be ap-
plied, and a number of procedures have been developed
for the stereoselective oxidation of sulfides.2 The sulfone
group has been recognized for its ability to stabilize an-
ions,3 radicals4 and for its ability to function as a leaving
group.4
We started to investigate this reaction by optimizing the
reaction conditions with phenyl acetylene (1) as the aryl-
acetylene component (Table 1).
Table 1 Optimization of the Reaction of Phenyl Acetylene (1) with
Sodium Sulfide (2)a
Ph
Ph
solvent
½ Na2S
+
S
Ph
temp
18 h
1
2
3
Entry Solvent Additive Temp (°C) Conversion (%)b,d
O
S
O
O
S
S
1
2
DMF
DMF
DMF
DMF
DMF
DMF
EtOH
EtOH
EtOH
DMA
–
24
40
70
24
40
70
24
40
70
70
–
R
R
R
R
R
R
–
14
I
II
III
3
–
31
Figure 1 Divinysulfide (I), divinylsulfoxide (II) and divinylsulfone
(III)
4
H2Oc
H2Oc
H2Oc
–
9
5
45
Especially, divinylsulfoxides and divinylsulfones (II and
III, Figure 1) display a highly diverse reactivity, because
the activation of the double bonds can be modulated by
the three oxidation states of the sulfur atom. The double
bonds are active in nucleophilic conjugate additions,5
which lead to the formation of chalcogen- and nitrogen-
6
77 (80)
7
–
2
8
–
9
–
20 (25; other isomers)
98 (80)
containing
heterocycles,6
sulfoxide-bridged
bisphosphines7 and addition products.8 Furthermore,
cyclopropanations9 and cycloadditions10 have also been
reported. Thus, synthesis of the corresponding divinylsul-
fides is of central interest because the sulfoxides and sul-
fones can generally be obtained using a suitable oxidation
10
H2Oc
a Using Na2S (1 M) in the corresponding solvent.
b Conversion to 3 determined by calibrated GC.
c Amount of additive: 2 equiv.
d Value in parentheses corresponds to the yield of 3 after purification
method.1,2 Generally, divinylsulfides are obtained either by column chromatography.
SYNTHESIS 2010, No. 6, pp 0947–0952
Advanced online publication: 04.01.2010
DOI: 10.1055/s-0029-1218625; Art ID: T20609SS
x
x
.
x
x
.2
0
1
0
We initially chose to use anhydrous dimethylformamide
(DMF) as solvent because of its ability to dissolve a wide
© Georg Thieme Verlag Stuttgart · New York

948
J. Paradies
PAPER
array of alkali salts. The reaction proceeded at elevated
temperatures (entries 2 and 3) and the bis(2-phenylvi-
nyl)sulfide (3) was formed in 31% yield at 70 °C. The ad-
dition of two equivalents of water led to a significant
increase in yield; the product was furnished in 45% yield
compared to 14% under anhydrous conditions (entries 2
and 5). Raising the reaction temperature from 40 °C to
70 °C resulted in an increase in the yield to give 3 in 77%
(entry 6). On a millimole scale (1 mmol), 3 was furnished
in 80% yield (compared to 67% yield using conditions re-
ported in the literature)14c as a mixture of diastereomers
(cis,cis to cis,trans ratio 5.5:1). This increase in the effi-
ciency of the process can be attributed to the partial hy-
drolysis of 2 to more active reagent sodium hydrosulfide
(NaSH; 4).15 Hence, the application of a protic solvent,
e.g. ethanol, should also provide 4 to a certain extent, and
would offer a less toxic alternative for this process. In-
deed, choosing ethanol as solvent at a temperature of
70 °C resulted in the formation of significant amounts of
3, together with some other isomers (entry 9). However,
dimethyl acetamide (DMA) was the solvent of choice, be-
cause both 2 and 4 are capable of cleaving DMF16 to form
thioformic acid and dimethylamine. The reaction still pro-
ceeded in good yield (entry 10) and the product was fur-
nished with the same isolated yield as that obtained in
DMF.
Table 2 Substrate Scope of the Reaction of 2 with Terminal
Alkynesa
R
R
H2O (2 equiv)
+
½ Na2S
S
R
DMA, 70 °C, 18 h
1.0 mmol
Entry
R
Product Yield
(%)b
Ratio of isomers
cis,cis/cis,transc
1
2
3
3
5
6
80
5.5:1
3:1
70
OMe
56d
8:1
MeO
H2N
4
5
7
8
59
5.5:1
57, 72e 1.5:1
N
6
7
9
85
4:1
Cl
10
11f
n.d.
The scope of the reaction was explored using the opti-
mized reaction conditions. We first investigated aryl-sub-
stituted terminal alkynes as suitable substrates (Table 2).
n-Hex
a Reaction conditions: 2 (1 M), DMA, 70 °C, 18 h.
b Average yield of two experiments after purification by column chro-
matography.
Generally, the reaction proceeds in good yield for both
electron-rich and electron-deficient aromatic alkynes.
Electron-withdrawing and electron-donating groups are
both tolerated in the ortho position (Table 2, entries 2, 3,
and 4). An electron-donating functionality in the para po-
sition retards the reaction and results in longer reaction
times (Table 2, entry 3). The chlorobenzene derivative
proved to be reactive under the reaction conditions and
provided the product in excellent yield (85%). Heterocy-
clic substrates, such as pyridyl-substituted alkynes, were
activated enough to allow the reaction to be performed
even at lower temperature (Table 2, entry 5).17 The reac-
tion proceeded sluggishly with unactivated alkynes such
as 1-octyne (Table 2, entry 7) and failed completely with
tert-butylacetylene. More activated alkynes, such as
p-cyanophenylacetylene or propynic ester, furnished oli-
gomeric and polymeric material. The divinylsulfides were
obtained after column chromatography as a mixture of
isomers. For the (2-arylvinyl)sulfides 3–9, the cis,cis-con-
c Determined by 1H NMR.
d The reaction was not carried to completion.
e The reaction was performed at r.t. for 48 h.
f Compound was characterized by GC-MS.
Oxone® (3 equiv)
acetone, r.t., 12 h
R
R
R
O
S
R
S
cis,cis/cis,trans
5.5:1
(3)
(5)
(9)
cis,cis-11, 89%
cis,cis-12, 58%
cis,cis-13, 44%
R = Ph
3:1
o-anisyl
m-chlorobenzene
4:1
Scheme 1 Oxidation of divinylsulfides to the divinylsulfoxides
yields were obtained when electron-rich (5) or electron-
poor (9) divinylsulfides were employed (as mixtures of
isomers). The configuration of the double bond was re-
tained, which was easily observed by 1H NMR spectros-
copy (the vicinal coupling constant was 10 Hz, which is in
the typical range for Z-olefins).
1
figuration of the double bond was observed by H NMR
spectroscopy to constitute the major isomer (Table 2).
The direct oxidation of 3 to the corresponding sulfone 14
could be achieved by the reaction of the sulfide, as a mix-
ture of isomers, with m-chloroperbenzoic acid
(MCPBA)19 in 59% yield after column chromatography
(Scheme 2). The predominant Z-configuration of the dou-
ble bond was conserved as the major diastereomer
(J = 12.1 Hz for the vinylic protons).
The products are valuable substrates for further derivati-
zation, for example, oxidation to the sulfoxides and sul-
fones. The oxidation of the 5.5:1 mixture of double bond
isomers of 3 with two equivalents of Oxone® yielded the
symmetric sulfoxide 11 (Scheme 1).5,18
After column chromatography, the cis,cis divinylsulfox-
ide 11 was furnished in excellent yield of 89%. Lower
Synthesis 2010, No. 6, 947–952 © Thieme Stuttgart · New York

PAPER
Divinylsulfides
949
cis,cis-Diastereomer
MCPBA
13C NMR (CDCl3, 100.1 MHz): d = 136.4, 128.9, 128.6, 127.3,
(10 equiv)
R
R
R
R
O2
S
S
127.0, 126.2.
r.t., CHCl3
cis,cis/cis,trans
cis,cis/cis,trans
cis,trans-Diastereomer
5.5:1
3:1
3:1
3:1
6:1
13C NMR (CDCl3, 100.1 MHz): d = 136.6, 136.5, 129.9, 128.9,
128.5, 127.7, 127.5, 126.0, 124.1, 124.0 (two carbon atoms were not
detected).
R = Ph
(3)
(5)
14, 59%
15, 56%
16, 54%
o-anisyl
4:1
m-chlorobenzene (9)
Scheme 2 Oxidation of divinylsulfides to divinylsulfones
IR (DRIFT): 3057 (s), 3022 (s), 2926 (m), 2594 (w), 2317 (w), 1947
(m), 1869 (m), 1680 (m), 1593 (s), 1490 (s), 1444 (s), 1345 (s), 1075
(m), 944 (m), 834 (s), 772 (s), 681 (s), 521 (s) cm–1.
The yields for electron-rich and electron-poor divinylsul-
fones 15 and 16 were 56% and 54%, respectively, indicat-
ing that the electronic substitution pattern does not
influence the oxidation process substantially.
HRMS: m/z calcd for C16H14S: 238.0816; found: 238.015.
Anal. Calcd for C16H14S: C, 80.63; H, 5.92; S, 13.45. Found: C,
80.34; H, 5.74; S, 13.90.
The pyridyl-substituted sulfide 8 contains three heteroat-
oms that are arranged appropriately for metal coordina-
tion,20,21 however, only the saturated derivative has been
reported in the literature so far.20 The unsaturated com-
pound 8 has a more rigid structure, which results in a
smaller bite-angle of the N-S-donor atoms. This new
framework should lead to new developments in the coor-
dination chemistry of N,S,N-tridentate ligands.
Bis[2-(2-anisyl)vinyl]sulfide (5)
According to typical procedure A, compound 5 was isolated from
the reaction of 2-methoxyphenylacetylene (264 mg, 2.0 mmol),
Na2S (78 mg, 1.0 mmol) and H2O (36 mg, 2.0 mmol) in DMA (1
mL).
Yield: 70% (195 mg, 65% first run; 223 mg, 75% second run); yel-
low oil; mixture of diastereomers: cis,cis to cis,trans, 3:1.
1H NMR (CDCl3, 400.1 MHz): d = 7.62 (dd, J = 1.6, 7.6 Hz, 2 H,
Ar-Hcis,cis), 7.36 (dd, J = 1.6, 7.6 Hz, 1 H, Ar-Hcis,trans), 7.32–7.23
(m, 4 H, Ar-H), 7.08–6.88 (m, 4 H, Ar-H), 6.84 (d, J = 10.8 Hz,
2 H, C=CHcis,cis), 6.56 (d, J = 10.4 Hz, 1 H, C=CHcis,trans), 6.44 (d,
J = 10.8 Hz, 2 H, C=CHcis,cis), 3.89 (s, 3 H, CH3Ocis,trans), 3.88 (s,
3 H, CH3Ocis,trans), 3.87 (s, 6 H, CH3Ocis,cis).
In conclusion, we have established a protocol for the gen-
eration of bis(arylvinyl)sulfides, which is complementary
to known procedures with respect to starting materials and
the scope of the reaction. The addition of sodium sulfide
to arylacetylenes furnishes the corresponding bis(arylvi-
nyl)sulfides in good to excellent yield. The sulfides can be
converted chemoselectively into the sulfoxides and sul-
fones. These substances can serve as valuable substrates
for further derivatizations such as cycloadditions, hydro-
genations and cross-coupling reactions. The pyridyl-
cis,cis-Diastereomer
13C NMR (CDCl3, 100.1 MHz): d = 156.2, 129.2, 128.6, 126.3,
125.3, 121.6, 120.3, 110.4, 55.5.
cis,trans-Diastereomer
13C NMR (CDCl3, 100.1 MHz): d = 156.6, 156.4, 134.2, 130.3,
substituted divinylsulfide could act as tridentate ligand for 129.3, 128.4, 126.9, 124.9, 124.8, 128.6, 124.4, 122.2, 120.7, 120.2,
transition metals and should form a more rigid scaffold
110.9, 110.6, 55.7, 55.5.
than the corresponding saturated sulfides.
IR (DRIFT): 3284 (w), 3033 (w), 2939 (m), 2045 (w), 1897 (w),
1596 (s), 1568 (m), 1484 (s), 1461 (s), 1435 (m), 1290 (m), 1246
(vs), 1179 (m), 1163 (m), 1109 (s), 934 (w), 750 (vs), 583 (w), 496
(w) cm–1.
Synthesis of Bis(2-phenylvinyl)sulfide (3); Typical Procedure A
A vial was charged with Na2S (382 mg, 4.89 mmol) and DMA (5
mL) was added to form a 1 M solution. The vial was sealed and
treated with ultrasound (Bandelin, SONOREX, TK 524) at r.t. for
30 sec. H2O (2 equiv, 176 mL, 176 mg, 9.79 mmol), followed by
phenyl acetylene (1.00 g, 9.79 mmol), were added by syringe. The
mixture was stirred at 70 °C for 18 h. After cooling to r.t., the mix-
ture was diluted with EtOAc (100 mL) and washed with H2O
(3 × 100 mL). The organic phase was dried over MgSO4, filtered
and the solvent was removed in vacuo. The residue was purified by
column chromatography (hexane–EtOAc, 20:1) to give the divinyl-
sulfide (3).
HRMS: m/z calcd for C18H18O2S: 298.1028; found: 298.1029.
Anal. Calcd for C18H18O2S: C, 72.45; H, 6.08; S, 10.75. Found: C,
72.93; H, 6.00; S, 10.39.
Bis[2-(4-anisyl)vinyl]sulfide (6)
According to typical procedure A, compound 6 was isolated from
the reaction of 4-methoxyphenylacetylene (264 mg, 2.0 mmol),
Na2S (78 mg, 1.0 mmol) and H2O (36 mg, 2.0 mmol).
Yield: 56% (157 mg, 53% first run; 177 mg, 59% second run); yel-
low oil; mixture of diastereomers: cis,cis to cis,trans, 8:1.
1H NMR (CDCl3, 400.1 MHz): d = 7.38 (d, J = 8.8 Hz, 4 H, Ar-H),
6.86 (d, J = 8.8 Hz, 4 H, Ar-H), 6.41 (d, J = 10.7 Hz, 2 H, C=CH),
6.25 (d, J = 10.7 Hz, 2 H, C=CH), 3.75 (s, 6 H, CH3O).
13C NMR (CDCl3, 100.1 MHz): d = 158.6, 130.2, 129.2, 126.3,
123.7, 113.9, 55.3.
Yield: 80% (949 mg, 80% first run; 932 mg, 80% second run); yel-
low oil; mixture of diastereomers: cis,cis to cis,trans, 5.5:1.
1H NMR (CDCl3, 400.1 MHz): d = 7.61 (m, 4 H, Ar-Hcis,cis), 7.50
(m, 4 H, Ar-H), 7.43 (m, 4 H, Ar-Hcis,trans), 7.37 (m, 2 H, Ar-Hcis,cis),
6.93 (d, J = 15.6 Hz, 1 H, C=CHcis,trans), 6.79 (d, J = 15.6 Hz, 1 H,
C=CHcis,trans), 6.71 (d, J = 10.7 Hz, 1 H, C=CHcis,trans), 6.65 (d,
J = 10.8 Hz, 2 H, C=CHcis,cis), 6.37 (d, J = 10.7 Hz, 1 H,
C=CHcis,trans), 6.46 (d, J = 10.8 Hz, 2 H, C=CHcis,cis).
IR (DRIFT): 3284 (w), 3033 (w), 2939 (m), 2834 (m), 1596 (s),
1568 (s), 1484 (vs), 1461 (vs), 1435 (s), 1246 (vs), 1163 (w,) 1109
(m), 1027 (s), 750 (vs), 496 (w) cm–1.
HRMS: m/z calcd for C18H18O2S: 298.1028; found: 298.1029.
Anal. Calcd for C18H18O2S: C, 72.45; H, 6.08; S, 10.75. Found: C,
72.28; H, 5.91; S, 10.76.
Synthesis 2010, No. 6, 947–952 © Thieme Stuttgart · New York

950
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PAPER
Bis[2-(3-aminophenyl)vinyl]sulfide (7)
cis,trans-Diastereomer
According to Typical Procedure A, compound 7 was isolated from
the reaction of 3-aminophenylacetylene (234 mg, 2.0 mmol), Na2S
(78 mg, 1.0 mmol) and H2O (36 mg, 2.0 mmol).
13C NMR (CDCl3, 100.1 MHz): d = 138.1, 137.9, 134.7, 134.3,
130.0, 129.6, 128.7, 128.3, 127.5, 127.3, 126.9, 126.3, 125.8, 125.3,
125.2, 124.1.
Yield: 56% (141 mg, 53% first run; 158 mg, 59% second run);
brown oil; mixture of diastereomers: cis,cis to cis,trans, 5.5:1.
1H NMR (CDCl3, 400.1 MHz): d = 7.10 (t, J = 7.6 Hz, 2 H, Ar-H),
6.83 (d, J = 7.6 Hz, 2 H, Ar-H), 6.75 (m, 2 H, Ar-H), 6.54–6.50 (m,
2 H, Ar-H), 6.38 (d, J = 10.8 Hz, 2 H, C=CH), 6.25 (d, J = 10.8 Hz,
2 H, C=CH), 3.46 (br, 4 H, NH2).
IR (DRIFT): 3035 (m), 2924 (w), 1936 (w), 1859 (w), 1590 (s),
1560 (s), 1476 (s), 1408 (s), 1346 (s), 1178 (m), 995 (m), 934 (m),
880 (s), 785 (vs), 753 (s), 671 (s), 559 (m), 451 (m) cm–1.
HRMS: m/z calcd for C16H12Cl2S: 306.0037; found: 306.0040.
Anal. Calcd for C16H12Cl2S: C, 62.55; H, 3.94; S, 10.44. Found: C,
63.06; H, 3.95; S, 9.44.
13C NMR (CDCl3, 100.1 MHz): d = 146.4, 137.3, 129.3, 127.0,
126.1, 119.4, 115.2, 114.3.
Synthesis of cis,cis-Bis(2-phenylvinyl)sulfoxide (11); Typical
Procedure B
IR (DRIFT): 3430 (s), 3352 (s), 3214 (s), 3032 (m), 1600 (vs), 1494
(s), 1442 (m), 1319 (m), 1167 (m), 993 (w), 865 (m), 782 (s), 680
(m), 465 (w) cm–1.
To a solution of a diastereomeric mixture (5.5:1) of 3 (756 mg, 3.17
mmol) in acetone (76 mL), Oxone (3 equiv, 5.86 g, 9.52 mmol) dis-
solved in H2O (29 mL) was added dropwise. The mixture was
stirred at r.t. for 24 h then the mixture was diluted with EtOAc (50
mL) and H2O (100 mL). The organic layer was separated and the
aqueous layer was extracted with EtOAc (3 × 50 mL). The com-
bined organic layer was dried over MgSO4, filtered, and the solvent
was removed in vacuo. The cis,cis-divinylsulfoxides were separated
from small amounts of the cis,trans isomer by column chromatog-
raphy (SiO2; EtOAc–hexane, 1:3→1:1→3:1).
HRMS: m/z calcd for C16H16N2S: 268.1034; found: 268.1037.
Bis[2-(2-pyridyl)vinyl]sulfide (8)
According to Typical Procedure A, compound 8 was isolated from
the reaction of 2-pyridylacetylene (234 mg, 2.0 mmol), Na2S (78
mg, 1.0 mmol) and H2O (36 mg, 2.0 mmol).
Yield: 57% (136 mg, 57% first run; 136 mg, 57% second run); off-
white solid; mixture of diastereomers: cis,cis to cis,trans, 1.5:1.
Yield: 89% (718 mg, 2.82 mmol); white solid; mp 95 °C.
1H NMR (CDCl3, 400.1 MHz): d = 8.70–8.62 (m, 3 H, Ar-H), 8.50–
8.44 (m, 1 H, Ar-Hcis,trans), 7.62–7.50 (m, 4 H, Ar-H), 7.25 (m, 2 H,
Ar-Hcis,cis), 7.16 (m, 1 H, Ar-Hcis,trans), 7.07 (m, 1 H, Ar-Hcis,trans),
7.05–7.7.00 (m, 3 H, Ar-H), 6.81 (d, J = 10.4 Hz, 1 H,
C=CHcis,trans), 6.68 (d, J = 15.8 Hz, 1 H, C=CHcis,trans), 6.67 (d,
J = 10.7 Hz, 2 H, C=CHcis,cis), 6.52 (d, J = 10.7 Hz, 2 H,
C=CHcis,cis).
1H NMR (CDCl3, 400.1 MHz): d = 7.50–7.10 (m, 10 H, Ar-H), 7.03
(d, J = 9.6 Hz, 2 H, C=CHcis,cis), 6.71 (d, J = 15.6 Hz, 1 H,
C=CHcis,trans), 6.52 (d, J = 9.6 Hz, 2 H, C=CHcis,cis).
13C NMR (CDCl3, 100.1 MHz): d = 138.5, 135.1, 133.8, 129.6,
129.4, 128.5.
IR (DRIFT): 3054 (m), 3016 (m), 2923 (w), 2029 (w), 1955 (w),
1888 (w), 1761 (m), 1600 (m), 1570 (m), 1443 (s), 1022 (s), 787 (s),
693 (m), 540 (m) cm–1.
HRMS: m/z [M + H]+ calcd for C16H15OS: 255.0843; found:
cis,cis-Diastereomer
13C NMR (CDCl3, 100.1 MHz): d = 155.4, 149.1, 136.0, 134.7,
124.6, 123.6, 120.8.
255.0842.
Anal. Calcd for C16H14OS: C, 75.55; H, 5.55; S, 12.61. Found: C,
75.79; H, 5.54; S, 12.47.
cis,trans-Diastereomer
Mp 129 °C.
13C NMR (CDCl3, 100.1 MHz): d = 154.5, 149.6, 148.7, 136.7,
cis,cis-Bis[2-(2-anisyl)vinyl]sulfoxide (12)
136.1, 133.5, 130.5, 127.2, 123.8, 123.7, 121.8, 121.7.
According to Typical Procedure B, compound 12 was obtained
from the reaction of 5 (195 mg, 0.65 mmol; mixture of cis,cis and
cis,trans diastereomers, 3:1) and Oxone (1.19 g, 1.95 mmol).
IR (DRIFT): 3007 (m), 2327 (w), 1772 (w), 1735 (w), 1589 (vs),
1545 (vs), 1470 (vs), 1425 (s), 1353 (s), 1215 (m), 1151 (m), 1095
(m), 991 (m), 944 (m), 800 (vs), 746 (s), 540 (m) cm–1.
Yield: 58% (119 mg, 0.38 mmol); isomerically pure white solid
HRMS: m/z calcd for C14H12N2S: 240.0721; found: 240.0718.
(only cis,cis diastereomer); mp 106 °C.
Anal. Calcd for C14H12N2S: C, 69.97; H, 5.03; N, 11.66; S, 13.34.
Found: C, 69.82; H, 4.97; N, 11.67; S, 13.26.
1H NMR (CDCl3, 400.1 MHz): d = 7.30–7.17 (m, 4 H, Ar-H,
C=CHcis,cis), 7.02 (dd, J = 7.7, 1.5 Hz, 2 H, Ar-H), 7.79 (d, 2 H,
J = 7.8 Hz, Ar-H), 6.57 (m, 2 H, Ar-H), 6.51 (d, J = 10.5 Hz, 2 H,
C=CHcis,cis), 3.73 (s, 6 H, CH3O).
Bis[2-(3-chlorophenyl)vinyl]sulfide (9)
According to Typical Procedure A, compound 9 was isolated from
the reaction of 3-chlorophenylacetylene (234 mg, 2.0 mmol), Na2S
(78 mg, 1.0 mmol) and H2O (36 mg, 2.0 mmol).
13C NMR (CDCl3, 100.1 MHz): d = 157.3, 135.0, 134.2, 131.2,
130.8, 123.1, 120.2, 110.4, 55.5.
IR (DRIFT): 3054 (w), 3014 (m), 2952 (m), 2835 (m), 2535 (w),
2042 (w), 1911 (w), 1594 (s), 1483 (s), 1468 (s), 1435 (s), 1306 (s),
1034 (s), 1017 (s), 976 (s), 758 (s), 725 (m) cm–1.
HRMS: m/z [M + H]+ calcd for C18H19O3S: 315.1055; found:
Yield: 85% (253 mg, 82% first run; 272 mg, 89% second run); yel-
low oil; mixture of diastereomers: cis,cis to cis,trans, 4:1.
1H NMR (CDCl3, 400.1 MHz): d = 7.45–7.10 (m, 16 H, Ar-H), 6.76
(d, J = 15.5 Hz, 2 H, C=CHcis,trans), 6.52 (d, J = 15.5 Hz, 2 H,
C=CHcis,trans), 6.41 (d, J = 10.8 Hz, 2 H, C=CHcis,cis), 6.34 (d,
J = 10.8 Hz, 2 H, C=CHcis,cis).
315.1052.
Anal. Calcd for C18H18O3S: C, 68.76; H, 5.77; S, 10.20. Found: C,
68.67; H, 5.79; S, 10.35.
cis,cis-Diastereomer
13C NMR (CDCl3, 100.1 MHz): d = 137.8, 134.4, 129.7, 128.7,
127.4, 127.2, 126.7, 125.9.
cis,cis-Bis[2-(3-chlorophenyl)vinyl]sulfoxide (13)
According to Typical Procedure B, compound 13 was obtained
from the reaction of 9 (272 mg, 0.88 mmol; mixture of cis,cis and
cis,trans diastereomers, 4:1) and Oxone (1.62 g, 2.64 mmol).
Synthesis 2010, No. 6, 947–952 © Thieme Stuttgart · New York

PAPER
Divinylsulfides
951
Yield: 44% (125 mg, 0.39 mmol); isomerically pure (only cis,cis
diastereomer); white solid; mp 59 °C.
C=CHcis,cis), 3.75 (s, 3 H, CH3Ocis,trans), 3.73 (s, 6 H, CH3Ocis,cis),
3.70 (s, 3 H, CH3Ocis,trans).
1H NMR (CDCl3, 400.1 MHz): d = 7.28–7.16 (m, 8 H, Ar-H), 6.99
(d, J = 10.7 Hz, 2 H, C=CHcis,cis), 6.57 (d, J = 10.7 Hz, 2 H,
C=CHcis,cis).
13C NMR (CDCl3, 100.1 MHz): d = 137.4, 136.2, 135.4, 134.7,
129.9, 129.6, 129.3, 127.6.
cis,cis-Diastereomer
13C NMR (CDCl3, 100.1 MHz): d = 157.4, 137.1, 132.2, 131.5,
129.9, 121.7, 120.2, 110.1, 55.5.
cis,trans-Diastereomer
13C NMR (CDCl3, 100.1 MHz): d = 158.7, 157.2, 139.4, 137.4,
132.3, 132.0, 131.3, 130.9, 130.8, 127.0, 121.9, 121.4, 120.7, 120.1,
111.1, 55.4 (two carbon atom resonances were not detected).
IR (DRIFT): 3073 (w), 3013 (m), 2926 (w), 2016 (w), 1591 (m),
1561 (m), 1474 (m), 1410 (m), 1410 (m), 1222 (w), 1178 (w), 1014
(s), 875 (m), 790 (s), 683 (s), 628 (m) cm–1.
HRMS: m/z [M + H]+ calcd for C16H13Cl2OS: 323.0064; found:
323.0066.
IR (DRIFT): 3046 (s), 2940 (s), 2838 (s), 2046 (w), 1702 (w), 1599
(s), 1485 (s), 1464 (s), 1437 (s), 1368 (m), 1293 (s), 1252 (s), 1109
(s), 1049 (m), 1024 (s), 876 (w), 756 (s), 676 (m), 581 (m), 552 (m),
518 (m), 473 (m) cm–1.
Anal. Calcd for C16H12Cl2OS: C, 59.45; H, 3.74; S, 9.92. Found: C,
59.48; H, 3.88; S, 9.61.
HRMS: m/z calcd for C18H18O4S: 330.0926; found: 330.0923.
Synthesis of Bis(2-phenylvinyl)sulfone (14); Typical Procedure
C
Anal. Calcd for C18H18O4S: C, 65.43; H, 5.49; S, 9.70. Found: C,
65.56; H, 5.53; S, 9.70.
To a solution of 3 (80 mg, 0.34 mmol; mixture of diastereomers,
5.5:1) in CHCl3 (5 mL), were added MCPBA (10 equiv, 586 mg, 3.4
mmol; 99% pure) in one portion. After 3 h the benzoic acid started
to precipitate and the mixture was stirred for an additional 12 h. The
mixture was diluted with EtOAc (10 mL) and sat. Na2CO3 (10 mL).
The organic phase was separated and the aqueous phase was ex-
tracted with EtOAc (3 × 10 mL). The combined organic phase was
dried over MgSO4, filtered and the solvent was removed in vacuo.
The residue was purified by column chromatography (SiO2; hex-
ane–EtOAc, 50:1) to give sulfone 14.
Bis[2-(3-chlorophenyl)vinyl]sulfone (16)
According to Typical procedure C, compound 16 was obtained
from the reaction of 9 (193 mg, 0.63 mmol; mixture of cis,cis and
cis,trans diastereomers, 4:1) and MCPBA (1.08 g, 6.30 mmol;
99%).
Yield: 54% (115 mg); light-yellow oil; mixture of diastereomers:
cis,cis to cis,trans, 6:1.
1H NMR (CDCl3, 400.1 MHz): d = 7.51–7.41 (m, 1 H, Ar-Hcis,trans),
7.42–7.36 (m, 4 H, Ar-Hcis,cis), 7.35–7.08 (m, Ar-Hcis,trans and cis,cis),
7.05 (d, J = 12.1 Hz, 1 H, C=CHcis,trans), 6.82 (d, J = 12.1 Hz, 2 H,
C=CHcis,cis), 6.60 (d, J = 15.0 Hz, 1 H, C=CHcis,trans), 6.50 (d,
J = 12.1 Hz, 1 H, C=CHcis,trans), 6.29 (d, J = 12.1 Hz, 2 H,
C=CHcis,cis).
Yield: 59% (54 mg); light-yellow oil; mixture of diastereomers:
cis,cis to cis,trans, 3:1.
1H NMR (CDCl3, 400.1 MHz): d = 7.55–7.51 (m, 1 H, Ar-Hcis,trans),
7.52–7.44 (m, 4 H, Ar-Hcis,cis), 7.37 (d, J = 14.7 Hz, 1 H,
C=CHcis,trans), 7.35 (m, 6 H, Ar-Hcis,cis), 7.08 (d, J = 12.1 Hz, 1 H,
C=CHcis,trans), 6.83 (d, J = 12.2 Hz, 2 H, C=CHcis,cis), 6.62 (d,
J = 15.4 Hz, 1 H, C=CHcis,trans), 6.46 (d, J = 12.1 Hz, 1 H,
C=CHcis,trans), 6.24 (d, J = 12.2 Hz, 2 H, C=CHcis,cis).
cis,cis-Diastereomer
13C NMR (CDCl3, 100.1 MHz): d = 140.2, 134.3, 134.0, 131.5,
130.1, 130.0, 129.6, 128.5.
cis,cis-Diastereomer
cis,trans-Diastereomer
13C NMR (CDCl3, 100.1 MHz): d = 141.6, 132.6, 130.5, 130.3,
13C NMR (CDCl3, 100.1 MHz): d = 142.7, 140.3, 135.1, 134.1,
134.0, 132.0, 131.2, 130.4, 129.8, 129.6, 128.2, 128.1, 127.1, 126.7
(two carbon atom resonances were not detected).
130.2, 128.3.
cis,trans-Diastereomer
IR (DRIFT): 3053 (s), 2929 (w), 1611 (s), 1592 (s), 1564 (s), 1474
(s), 1425 (m), 1299 (s), 1222 (m), 1164 (m), 1127 (s), 1079 (m), 973
(w), 867 (m), 793 (s), 731 (m), 679 (s), 566 (w), 518 (w), 456 (w)
cm–1.
HRMS: m/z [M + H]+ calcd for C16H13Cl2O2S: 339.0013; found:
339.0011.
13C NMR (CDCl3, 100.1 MHz): d = 143.8, 141.7, 132.6, 132.4,
131.2, 130.9, 130.1, 130.0, 129.0, 128.4, 126.0 (one carbon atom
resonance was not detected).
IR (DRIFT): 3053 (s), 2932 (w), 1709 (w), 1605 (s), 1574 (m), 1493
(s), 1447 (s), 1295 (s), 1122 (s), 857 (m), 778 (s), 690 (s), 543 (m)
cm–1.
Anal. Calcd for C16H12Cl2O2S: C, 56.65; H, 3.57; S, 9.45. Found: C,
57.16; H, 3.67; S, 8.95.
HRMS: m/z [M + H]+ calcd for C16H15O2S: 271.0797; found:
271.794.
Bis[2-(2-anisyl)vinyl)]sulfone (15)
Acknowledgment
According to Typical Procedure C, compound 15 was obtained
from the reaction of 5 (165 mg, 0.55 mmol; mixture of cis,cis and
cis,trans diastereomers, 3:1) and MCPBA (954 mg, 5.53 mmol;
99%).
The authors would like to acknowledge the Fonds der Chemischen
Industrie for a Liebig grant to J.P.
Yield: 56% (102 mg); light-yellow oil; mixture of diastereomers:
cis,cis to cis,trans, 3:1.
References
1H NMR (CDCl3, 400.1 MHz): d = 7.74–7.69 (m, 1 H, Ar-Hcis,trans),
7.70–7.65 (m, 2 H, Ar-Hcis,cis), 7.53 (d, J = 15.5 Hz, 1 H,
C=CHcis,trans), 7.32–7.12 (m, Ar-Hcis,trans and cis,cis), 7.14 (d, J = 11.9
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Synthesis 2010, No. 6, 947–952 © Thieme Stuttgart · New York

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Synthesis 2010, No. 6, 947–952 © Thieme Stuttgart · New York