Synthesis of (diphenylphosphinoyl)methyl vinyl sulfides, symmetric and asymmetric divinyl sulfides from bis[(diphenylphosphinoyl)methyl] sulfide

Article abstract of DOI:10.1055/s-0030-1259969

Convenient Horner-Wittig-based synthetic approaches to the preparation of (diphenylphosphinoyl)methyl vinyl sulfides as well as symmetrically and unsymmetrically substituted divinyl sulfides, are described. The syntheses involve the use of the easily avai

Full text of DOI:10.1055/s-0030-1259969

PAPER
1233
Synthesis of (Diphenylphosphinoyl)methyl Vinyl Sulfides, Symmetric and
Asymmetric Divinyl Sulfides from Bis[(diphenylphosphinoyl)methyl] Sulfide
Synthesis of
V
iny
l
l
and D
a
ivinyl Sulf
u
ides dio C. Silveira,*a Francieli Rinaldi,a Mariana M. Bassaco,a Rafael C. Guadagnin,b Teodoro S. Kaufmanc
a
Departamento de Química, Universidade Federal de Santa Maria, 97105.900, Santa Maria, RS, Brazil
Fax +55(55)32208754; E-mail: silveira@quimica.ufsm.br
b
c
Departamento de Ciências Exatas e da Terra, Universidade Federal de São Paulo, 09971.270, Diadema, SP, Brazil
Instituto de Química Rosario (IQUIR, CONICET-UNR), Suipacha 531, S2002 LRK Rosario, Argentina
Received 28 December 2010; revised 17 February 2011
phosphinoyl)methyl] sulfide (1) as a convenient source of
the chalcogen.
Abstract: Convenient Horner–Wittig-based synthetic approaches
to the preparation of (diphenylphosphinoyl)methyl vinyl sulfides as
well as symmetrically and unsymmetrically substituted divinyl sul-
fides, are described. The syntheses involve the use of the easily
available bis[(diphenylphosphinoyl)methyl] sulfide as a common
starting material and sodium hydride as base, in tetrahydrofuran.
Attention was first directed towards the synthesis of
(diphenylphosphinoyl)methyl sulfides. The starting sulfur
reagent 1 was efficiently prepared in three steps and 81%
overall yield as a bench-stable solid, by employing our
previously reported procedure.6
Key words: sulfur, Wittig reaction, alkenation, ketones, aldehydes
The challenge was to find reaction conditions that would
allow the transformation to be stopped after only one of
the two possible reactive positions of the starting sulfide
had reacted, thus minimizing further transformation of the
desired vinyl sulfide into a symmetrically substituted di-
vinyl sulfide-type product.
The important role played by organochalcogen com-
pounds in modern organic synthesis is due mainly to their
chemo-, regio-, and stereoselective reactions;1 they also
display some useful biological activities.2 Vinylic chalco-
genides are versatile compounds for the synthesis of vari-
ous substances and for the preparation of products or
materials with targeted properties.3 Most of the useful
strategies that have been devised to access these com-
pounds entail the formation of new C–C bonds;4 other re-
ported synthetic methods are either narrow in scope,
involve the use of starting materials that are not readily
available, or require expensive catalysts (Pd, Pt, Rh, Ru,
etc.).5 Therefore, simple and efficient synthetic methods
that allow access to these compounds are still needed.
In order to develop and optimize suitable reaction condi-
tions, initial experiments were carried out with limiting
amounts (1.1 equiv) of 4-tert-butyl cyclohexanone as a
model carbonyl compound, in a solid–liquid two-phase
system consisting of dichloromethane and a twofold mo-
lar excess of solid potassium hydroxide, to which 18-
crown-6 was added as phase-transfer catalyst.8 However,
this approach met with failure and none of the expected
product was recovered. The same outcome was observed
when the transformation was attempted at room tempera-
ture in a biphasic system of 50% aqueous sodium hydrox-
ide and dichloromethane to which triethyl benzyl-
ammonium chloride (TEBACl), as phase-transfer cata-
lyst, was added.9
We have previously reported the preparation and a prelim-
inary study of the reactivity of chalcogenyl phosphonates
and phosphane oxides, where the feasibility of preparing
(dipenylphosphinoyl)methyl vinyl chalcogenides, as well
as symmetrically and unsymmetrically substituted divinyl
sulfides, selenides and tellurides from the corresponding
(diphenylphosphinoyl)methyl chalcogenides, was dem-
onstrated.6
The use of organolithium reagents was deliberately avoid-
ed because, in the case of enolizable carbonyls, it is
known that they may react preferentially with the carbon-
yl moiety. This has been shown to result in poor yields of
vinyl sulfides, a problem that was partially solved by the
group of Stéphan.5b,10 On the other hand, carrying out the
reaction in benzene at room temperature with potassium
tert-butoxide as base, to which a catalytic amount of 18-
crown-6 was added, furnished exclusively the symmetri-
cally substituted divinyl sulfide (49% yield) within three
hours at room temperature.
Therefore, in continuation of these studies, as a result of
our interest in preparing new vinylic chalcogenides based
on the Wittig and Horner–Wittig reactions,7 and in order
to better determine the scope and limitations of our strat-
egy, here, we wish to report a more comprehensive study.
Moreover, we provide a detailed account of our efforts to-
wards the synthesis of (dipenylphosphinoyl)methyl vinyl
sulfides as well as symmetrically and unsymmetrically
substituted divinyl sulfides, employing bis[(diphenyl-
In view of the above outcome, a milder and more selective
reagent was sought. To our satisfaction, when the reaction
was performed with sodium hydride in tetrahydrofuran,
65% of the desired vinylic sulfide product was isolated af-
ter heating at 60 °C for 24 hours. However, because the
reaction with ketones and sodium hydride as the base is
heterogeneous, it was relatively slow. Therefore, the ef-
SYNTHESIS 2011, No. 8, pp 1233–1242
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x
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x
x
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0
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Advanced online publication: 24.03.2011
DOI: 10.1055/s-0030-1259969; Art ID: M57110SS
© Georg Thieme Verlag Stuttgart · New York

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C. C. Silveira et al.
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fect of adding 10% hexamethylphosphoramide (HMPA) Sulfide 1 was also reacted with aliphatic aldehydes, af-
to the reaction medium was tested; unfortunately, the effi- fording moderate yields (62–64%) of the corresponding
ciency of the transformation did not improve, and 63% of vinyl sulfides 3g and 3h (Table 1, entries 7 and 8), which
the expected vinyl sulfide was isolated.
were obtained as mixtures of geometric isomers (E/Z ~
4:1). As expected, these transformations were faster than
those involving ketones, being complete after three hours
at room temperature. Unfortunately, we were unable to
obtain the monosubstituted products resulting from aro-
matic aldehydes. This transformation is fast, and the reac-
tion conditions are not selective enough; the reaction rates
leading to the vinyl sulfide and to the related divinyl sul-
fide being similar. The latter sulfides were also isolated as
mixtures of geometric isomers.
The generality of the transformation was then evaluated
under the optimized conditions (Table 1). Thus, various
five- and six-membered ring ketones (2) were reacted
with 1, furnishing the corresponding vinyl sulfides 3a–d
in 65–69% yield (entries 1–4). However, under the same
conditions, cycloheptanone afforded the expected product
3e in 48% yield, while the use of benzophenone, as an ex-
ample of a more hindered carbonyl component, furnished
only 28% of the vinylic sulfide 3f and most of the unreact-
ed reagent 1 was recovered at the end of reaction.
On the other hand, despite alkyl vinyl sulfides being well-
characterized compounds, little is known about divinyl
sulfides, and synthetic approaches towards symmetrically
substituted divinyl sulfides are relatively scarce, some-
times inefficient and are often of unknown scope.5c,11 Di-
vinyl sulfide itself is a versatile starting material that can
Longer reaction times did not improve the yield of 3f. In
addition, it was observed that the use of larger amounts of
ketone or employing HMPA as a co-solvent only in-
creased the formation of the divinyl sulfide at the expense
of its monosubstituted congener 3f.
Table 1 Synthesis of (Diphenylphosphinoyl)methyl Vinyl Sulfides
R1R2CO (2)
NaH, THF
O
O
O
R1
R2
Ph2P
S
Ph2P
S
PPh2
1
3a–h
Entry
1
Time (h)
Temp (°C)
Product
Structure of the product
E/Z ratioa
Yield (%)
65
O
24
24
24
24
60
60
60
60
3a
Ph2P
S
S
S
t-Bu
O
2
3
4
3b
3c
3d
69
68
68
Ph2P
O
Ph2P
O
Ph2P
S
S
O
5
6
24
24
60
60
3e
3f
48
28
Ph2P
O
Ph2P
S
O
7
8
3
3
r.t.
r.t.
3g
3h
4:1
4:1
64
62
Ph2P
S
S
O
Ph2P
( )7
a Calculated from the corresponding 1H NMR spectra.
Synthesis 2011, No. 8, 1233–1242 © Thieme Stuttgart · New York

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Synthesis of Vinyl and Divinyl Sulfides
1235
be used for the preparation of a variety of organosulfur Ketones reacted more sluggishly, requiring the system to
compounds and has been recently employed for the syn- be heated at 60 °C for 24 hours. Cyclohexanone and its 4-
thesis of selenium and other heterocycles.12
substituted derivatives (Table 3, entries 7–9) gave the ex-
pected products in satisfactory yields (69–78%), while
benzophenone afforded 69% of the divinyl sulfide 4j;
however, this yield was attained after adding HMPA (0.1
equiv) to the reaction medium (Table 3, entries 10). Inter-
estingly, divinyl sulfide 4j was previously obtained by
Selzer and Rappoport in only 17% yield by reacting 2,2¢-
diphenylacetaldehyde with Lawesson’s reagent.14 On the
other hand, careful analysis of the 13C NMR spectra of
compounds 4h and 4i, which exhibited duplication of the
resonances of the olefinic carbons (Dd <0.05 ppm), con-
firmed their formation as ~1:1 diastereomeric mixtures of
structures having their methyl and tert-butyl substituents
on the same side and on different sides of the molecular
plane.
Therefore, by employing the optimized conditions for the
preparation of the vinylic sulfides as a starting point, the
outcome of the synthesis of the related symmetrically sub-
stituted divinyl sulfides was optimized with the same mo-
lar amounts of base and carbonyl component. In view of
the previously observed reactivity of aromatic aldehydes,
benzaldehyde was used as a model carbonyl compound.
As shown in Table 2, the best yields were attained when
tetrahydrofuran alone was employed as solvent (entry 3).
Addition of 10% (v/v) HMPA (entry 2) or performing the
transformation in a 1:1 toluene–tetrahydrofuran mixture
(entry 1) resulted in diminished product yields of 78 and
75%, respectively.
Approaches to the synthesis of unsymmetrically substitut-
ed divinyl sulfides are even scarcer than those leading to
their symmetric counterparts.15 Compounds bearing this
feature have been synthesized as irreversible inhibitors of
leukotriene biosynthesis16 and as intermediates in the
landmark synthesis of cobyric acid17 and the synthesis of
chlorins.18 Therefore, the preparation of unsymmetrically
substituted divinyl sulfides was undertaken, employing
vinyl sulfide 3a as the starting material (Table 4). It was
observed that the reactions with substituted benzalde-
hydes took place in good yields (78–85%) regardless of
the nature of the substituent (entries 1–4) and were com-
pleted at room temperature within three to four hours. In-
terestingly, the use of piperonal required a slightly longer
reaction time (entry 4).
Table 2 Optimization of the Synthesis of Symmetrically Substitut-
ed Divinyl Sulfides
PhCHO (3 equiv)
O
O
H
H
NaH (4 equiv)
S
Ph2P
S
PPh2
conditions
Ph
Ph
1
4a
Entry Solvent
1
Temp
Time
(h)
E,E/Z,E Yield
ratioa
(%)
toluene–THF (1:1)
r.t.
6
3:1
78
2
3
HMPA–THF (1:10) r.t.
THF r.t.
3
2:1
75
3
3.2:1
85
a Calculated from the corresponding 1H NMR spectra.
Following the previously observed trend, the use of buta-
nal and decanal as aliphatic aldehydes (Table 4, entries 5
and 6) provided the expected products, albeit in slightly
diminished yields (51 and 60%, respectively). On the oth-
er hand, compound 5g, which has two stereogenic centers,
was obtained as an approximately equimolar mixture of
diastereoisomers (entry 7), as evidenced by signal dupli-
cation in its 13C NMR spectrum. In addition, when ben-
zophenone was employed as the carbonyl component of
the transformation (entry 8), a moderate 54% yield of
product 5h was realized.
The generality of the transformation was studied with dif-
ferent aromatic and aliphatic aldehydes, as well as with
six-membered ring ketones and with benzophenone
(Table 3). As previously observed, reaction with benzal-
dehyde and its derivatives furnished mixtures of geomet-
ric isomers. However, an exception was observed in the
reaction with p-tolualdehyde in a mixture of toluene–
tetrahydrofuran as solvent. In this particular case, only the
E,E-isomer was produced (70% yield).
Unfortunately, the same selectivity was not observed for
the other aldehydes tested. The yields of these transforma-
tions (81–85%) clearly outperformed those of the aliphat-
ic aldehydes, which provided the symmetrical divinyl
sulfides in 38–44% yield. The reactions were complete
within three to four hours at room temperature and, in all
cases, the E,E-isomer was predominant.
In all examples, a clear preference for the E,E isomer was
1
observed by H and 13C NMR spectroscopy, which is in
agreement with the selectivity observed for other Horner–
Wittig reactions of phosphane oxides.19
Some of the synthesized (diphenylphosphinoyl)methyl vi-
nyl sulfides and divinyl sulfides exhibited interesting bio-
logical activity as inhibitors of lipid peroxidation induced
by sodium nitroprusside in rat brain and liver.20 These re-
sults will be communicated shortly.
Interestingly, recently, Gurasova et al. obtained distyryl
sulfide 4a by reaction of phenylacetylene with elemental
sulfur under microwave irradiation in 65% yield as a 2:1
mixture of the E,Z and Z,Z isomers. However, the gener-
ality of the transformation under these reaction conditions
was not further studied; this conversion rate represented a
considerable improvement over previously reported rates
for the same transformation (20% yield).13
In conclusion, we have devised simple, efficient, and
straightforward methods for the synthesis of (diphe-
nylphosphinoyl)methyl vinyl sulfides as well as symmet-
rically and unsymmetrically substituted divinyl sulfides
from bis[(diphenylphosphinoyl)methyl] sulfide. This
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C. C. Silveira et al.
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Table 3 Synthesis of Symmetrically Substituted Vinyl Sulfides
R1R2CO (3 equiv)
NaH (4 equiv), THF
O
O
R1
R2
R1
R2
S
Ph2P
S
PPh2
1
4a–j
Entry
1
Time (h)
Temp (°C)
r.t.
Product
Structure of the product
E,E/Z,E ratioa
Yield (%)
85
S
3
3
4a
3.2:1
S
2
3
r.t.
r.t.
4b
4c
6:1
82
84
S
4
3
3.8:1
MeO
OMe
S
4
r.t.
4d
3.3:1
81
Cl
Cl
S
S
5
6
3
4
r.t.
r.t.
4e
4f
1.3:1
1.2:1
44
38
( )7
( )7
S
7
8
9
24
24
24
60
60
60
4g
4h
4i
69
72
78
b
S
–
b
S
–
t-Bu
t-Bu
69c
S
10
24
60
4j
a Calculated from the corresponding 1H NMR spectra.
b Obtained as a ~1:1 mixture of diastereomers.
c HMPA (0.1 equiv) was added to the reaction medium.
compound may be regarded as a valuable new member of ly lower conversions when compared to their cyclohex-
a family of reagents capable of performing double Wittig anone-derived counterparts.
reactions.21 The transformations were optimized and con-
In general, aliphatic and aromatic aldehydes reacted at
ditions were found whereby formation of (diphenylphos-
room temperature, providing the expected products in
phinoyl)methyl vinyl sulfides took place in synthetically
moderate to good yields, with the aromatic aldehydes out-
useful yields, employing sodium hydride as base in tet-
performing their aliphatic counterparts. This resulted in
rahydrofuran. Use of cycloheptanone and benzophenone
notable yield differences when the symmetrically substi-
as the carbonyl components resulted in moderate to slight-
tuted divinyl sulfides were prepared.
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Synthesis of Vinyl and Divinyl Sulfides
1237
Table 4 Synthesis of Unsymmetrically Substituted Divinyl Sulfides
R1R2CO
O
NaH (2 equiv)
THF
R1
R2
S
Ph2P
S
t-Bu
t-Bu
3a
5a–h
Entry
1
Time (h)
3
Temp (°C)
r.t.
Product
Structure of the product
E/Z ratio
Yield (%)
S
t-Bu
5a
12:1
78
85
85
MeO
S
t-Bu
2
3
4
3
4
r.t.
r.t.
r.t.
5b
5c
5d
10:1
4:1
S
t-Bu
Cl
S
t-Bu
12
10:1
82
O
O
S
5
6
7
3
3
r.t.
r.t.
60
5e
5f
1:1
1:1
51
60
81
t-Bu
t-Bu
S
( )7
a
S
24
5g
–
t-Bu
S
8
24
60
5h
54
t-Bu
a Obtained as a ~1:1 mixture of diastereoisomers.
Melting points were recorded with an MQAPF-301 instrument and
are reported uncorrected. Infrared spectra were recorded with a
Nicolet–Magna spectrometer. The 1H (400 and 200 MHz) and 13C
(100 and 50 MHz) NMR spectra were recorded with Bruker DPX
400 and DPX 200 instruments, using CDCl3 as solvent. Chemical
shifts (d) are expressed in ppm downfield from internal tetrameth-
ylsilane or CHCl3, and J values are given in Hz. Elemental analyses
were carried out with a Perkin–Elmer 2400 instrument. All reac-
tions were performed in flame-dried glassware under a positive
pressure of argon. Air- and moisture-sensitive reagents and solvents
were transferred by using a syringe, and were introduced into the re-
action vessels through rubber septa. All the reactions were moni-
tored by thin layer chromatography (TLC) carried out using Merck
60 F254 plates with a 0.25 mm thickness. Column chromatography
was carried out using Merck silica gel 60 (230–400 mesh). Reagents
were used as received. Aldehydes and ketones were distilled before
their use; anhydrous THF was distilled from Na-benzophenone
ketyl. All new compounds gave single spots on TLC plates run in
different hexane–EtOAc solvent systems. TLC plates were visual-
ized with UV light (254 nm) or by spraying with methanolic aniline/
sulfuric acid reagent and careful heating.
(Diphenylphosphinoyl)methyl Vinyl Sulfides 3a–f; General
Procedure
NaH (dry 95%; 51 mg, 2 mmol) was added to a solution of
bis[(diphenylphosphinoyl)methyl] sulfide (462 mg, 1 mmol) in
THF (10 mL) at r.t. After 20 min, the appropriate carbonyl com-
pound (1.1 mmol) was added and the system was stirred for 24 h at
60 °C (oil bath temperature). The reaction was cooled to r.t., sat. aq
NH4Cl (20 mL) was added and the mixture was extracted with
Synthesis 2011, No. 8, 1233–1242 © Thieme Stuttgart · New York

1238
C. C. Silveira et al.
PAPER
CH2Cl2 (3 × 20 mL). The organic layer was dried (MgSO4), filtered,
and concentrated under reduced pressure, and the residue was puri-
fied by column chromatography (CH2Cl2–hexanes–EtOAc, 1:5:4).
1H NMR (400 MHz, CDCl3): d = 1.52–1.64 (m, 4 H), 2.08–2.17 (m,
4 H), 3.39 (d, JP–H = 8.1 Hz, 2 H), 5.70–5.71 (m, 1 H), 7.45–7.49
(m, 4 H), 7.52–7.56 (m, 2 H), 7.77–7.82 (m, 4 H).
13C NMR (100 MHz, CDCl3): d = 26.1, 26.5, 30.6, 32.4 (d, JP–C
69.9 Hz), 34.0, 112.2 (d, JP–C = 2.8 Hz), 128.5 (d, JP–C = 11.7 Hz),
=
(Diphenylphosphinoyl)methyl[(4-tert-butylcyclo-
hexylidene)methyl]sulfide (3a)6
Yield: 65%; mp 177–179 °C.
IR (KBr): 1192 (P=O), 1436, 1618 cm–1.
1H NMR (200 MHz, CDCl3): d = 0.82 (s, 9 H), 0.86–1.16 (m, 3 H),
1.53–1.97 (m, 4 H), 2.13–2.20 (m, 1 H), 2.68–2.75 (m, 1 H), 3.39
(d, JP–C = 8.3 Hz, 2 H), 5.55 (s, 1 H), 7.42–7.59 (m, 6 H), 7.75–7.85
(m, 4 H).
131.3 (d, JP–C = 9.5), 131.8 (d, JP–C = 101.0 Hz), 132.0 (d, JP–C
=
2.7 Hz), 148.0.
GC-MS (EI): m/z (%) = 328 (9) [M+], 326 (20), 324 (35), 278 (64),
250 (47), 205 (100), 146 (32), 72 (63).
Anal. Calcd for C19H21OPS: C, 69.49; H, 6.45. Found: C, 68.92; H,
6.36.
13C NMR (100 MHz, CDCl3): d = 27.5, 27.6, 28.5, 29.8, 32.3, 32.5
(d, JP–C = 69.4 Hz), 35.9, 47.8, 113.6 (d, JP–C = 2.8 Hz), 128.4 (d,
JP–C = 11.3 Hz), 128.5 (d, JP–C = 12.0 Hz), 131.2 (d, JP–C = 9.2 Hz),
131.3 (d, JP–C = 9.2 Hz), 131.6 (d, JP–C = 103.3 Hz), 131.8 (d,
JP–C = 103.3 Hz), 132.0 (d, JP–C = 2.8 Hz), 144.3.
GC-MS (EI): m/z (%) = 398 (1) [M+], 249 (8), 248 (10), 216 (48),
215 (100), 91 (10), 57 (12), 41 (15).
(Diphenylphosphinoyl)methyl[(cycloheptylidenemethyl)meth-
yl]sulfide (3e)
Yield: 48%; mp 139–141 °C.
IR (KBr): 536, 704, 1122, 1190 (P=O), 1437 cm–1.
1H NMR (200 MHz, CDCl3): d = 1.39–1.50 (m, 8 H), 2.03–2.19 (m,
4 H), 3.40 (d, JP–H = 8.2 Hz, 2 H), 5.60 (s, 1 H), 7.46–7.56 (m, 6 H),
7.75–7.85 (m, 4 H).
Anal. Calcd for C24H31OPS: C, 71.78; H, 7.63. Found: C, 72.33; H,
7.84.
13C NMR (100 MHz, CDCl3): d = 26.3, 28.6, 29.0, 29.7, 31.6, 32.2
(d, JP–C = 69.5 Hz), 36.9, 117.2 (d, JP–C = 2.9 Hz), 128.3 (d, JP–C
=
11.7 Hz), 131.1 (d, JP–C = 8.8 Hz), 131.6 (d, JP–C = 101.0 Hz), 131.8
(d, JP–C = 2.9 Hz), 144.8.
GC-MS (EI): m/z (%) = 356 (1) [M]+, 216 (46), 215 (100), 201 (28),
(Diphenylphosphinoyl)methyl(cyclohexylidenemethyl)sulfide
(3b)
Yield: 69%; mp 148–150 °C.
IR (KBr): 539, 1191 (P=O), 1439 cm–1.
1H NMR (200 MHz, CDCl3): d = 1.40–1.50 (m, 6 H), 1.95–2.20 (m,
4 H), 3.38 (d, JP–H = 8.3 Hz, 2 H), 5.57 (s, 1 H), 7.42–7.58 (m, 6 H),
7.75–7.84 (m, 4 H).
13C NMR (100 MHz, CDCl3): d = 26.1, 26.9, 27.8, 30.0, 32.5 (d,
JP–C = 69.7 Hz), 36.1, 113.9 (d, JP–C = 3.2 Hz), 128.4 (d, JP–C
183 (10), 152 (6), 91 (22), 77 (50).
Anal. Calcd for C21H25OPS: C, 70.76; H, 7.07. Found: C, 71.11; H,
7.15.
(Diphenylphosphinoyl)methyl(2,2-diphenylvinyl)sulfide (3f)
Yield: 28%; mp 174–176 °C.
IR (KBr): 534, 699, 1187 (P=O), 1437 cm–1.
1H NMR (400 MHz, CDCl3): d = 3.47 (d, JP–H = 7.8 Hz, 2 H), 6.66
(s, 1 H), 7.05–7.07 (m, 2 H), 7.16–7.24 (m, 5 H), 7.28–7.36 (m,
3 H), 7.44–7.49 (m, 4 H), 7.51–7.56 (m, 2 H), 7.75–7.80 (m, 4 H).
13C NMR (100 MHz, CDCl3): d = 32.4 (d, JP–C = 69.0 Hz), 124.2 (d,
=
11.8 Hz), 131.2 (d, JP–C = 9.1), 131.8 (d, JP–C = 100.0 Hz), 131.9 (d,
JP–C = 2.6 Hz), 144.5.
GC-MS (EI): m/z (%) = 342 (5) [M+], 248 (6), 216 (51), 215 (100),
201 (10), 91 (11), 77 (14), 47 (7).
Anal. Calcd for C20H23OPS: C, 70.15; H, 6.77. Found: C, 70.03; H,
6.79.
JP–C = 2.3 Hz), 127.0, 127.6, 128.1, 128.2, 128.6 (d, JP–C
11.5 Hz), 129.6, 131.3 (d, JP–C = 9.2 Hz), 131.4 (d, JP–C
101.2 Hz), 132.2 (d, JP–C = 2.3 Hz), 138.8, 140.1, 141.1.
=
=
(Diphenylphosphinoyl)methyl[(4-methylcyclohexylidene)meth-
yl]sulfide (3c)
Yield: 68%; mp 150–152 °C.
GC-MS (EI): m/z (%) = 426 (25) [M]+, 216 (42), 215 (100), 201 (9),
178 (10), 91 (16), 77 (12), 51 (8).
IR (KBr): 536, 718, 1190 (P=O), 1437 cm–1.
1H NMR (200 MHz, CDCl3): d = 0.74–0.95 (m, 5 H), 1.32–1.76 (m,
4 H), 1.85–2.15 (m, 2 H), 2.60–2.67 (m, 1 H), 3.38 (d, JP–H
8.3 Hz, 2 H), 5.57 (s, 1 H), 7.42–7.58 (m, 6 H), 7.75–7.84 (m, 4 H).
13C NMR (100 MHz, CDCl3): d = 21.7, 29.2, 32.1, 32.5 (d, JP–C
69.8 Hz), 34.9, 35.4, 35.9, 114.0 (d, JP–C = 2.9 Hz), 128.4 (d, JP–C
11.7 Hz), 128.4 (d, JP–C = 11.7 Hz), 131.2 (d, JP–C = 9.4 Hz), 131.2
(d, JP–C = 9.1 Hz), 131.6 (d, JP–C = 101.0 Hz), 131.8 (d, JP–C
101.0 Hz), 131.9 (d, JP–C = 2.9 Hz), 144.0.
Anal. Calcd for C27H23OPS: C, 76.03; H, 5.44. Found: C, 76.01; H,
5.44.
=
(Diphenylphosphinoyl)methyl Vinyl Sulfides 3g,h; General
Procedure
=
=
NaH (dry 95%; 51 mg, 2 mmol) was added to a solution of
bis[(diphenylphosphinoyl)methyl] sulfide (462 mg, 1 mmol) in
THF (10 mL) at r.t. After 20 min, the appropriate carbonyl com-
pound (1.5 mmol) was added and the reaction was stirred for 3 h.
Sat. aq NH4Cl (20 mL) was added and the mixture was extracted
with CH2Cl2 (3 × 20 mL). The organic layer was dried (MgSO4),
filtered, and concentrated under reduced pressure. The residue was
purified by column chromatography (CH2Cl2–hexanes–EtOAc,
1:5:4).
=
GC-MS (EI): m/z (%) = 356 (2) [M+], 216 (47), 215 (100), 125 (7),
91 (15), 77 (16).
Anal. Calcd for C21H25OPS: C, 70.76; H, 7.07. Found: C, 70.81; H,
7.03.
(Diphenylphosphinoyl)methyl(pent-1-enyl)sulfide (3g)
Yield: 64%; mp 73–75 °C; E/Z ratio = 4:1.
IR (KBr): 533, 691, 1187 (P=O), 1438 cm–1.
1H NMR (400 MHz, CDCl3): d (E-isomer) = 0.84 (t, J = 7.3 Hz,
3 H), 1.30 (sext., J = 7.3 Hz, 2 H), 1.94 (q, J = 7.1 Hz, 2 H), 3.40 (d,
JP–H = 8.8 Hz, 2 H), 5.64 (dt, J = 14.9, 7.1 Hz, 1 H), 5.90 (d, J =
14.9 Hz, 1 H), 7.45–7.56 (m, 6 H), 7.77–7.82 (m, 4 H).
(Diphenylphosphinoyl)methyl(cyclopentylidenemethyl)sulfide
(3d)
Yield: 68%; mp 143–145 °C.
IR (KBr): 534, 698, 1189 (P=O), 1437 cm–1.
Synthesis 2011, No. 8, 1233–1242 © Thieme Stuttgart · New York

PAPER
Synthesis of Vinyl and Divinyl Sulfides
1239
13C NMR (100 MHz, CDCl3): d (E-isomer) = 13.5, 22.1, 31.6 (d,
Bis(4-methoxystyryl)sulfide (4c)
JP–C = 69.5 Hz), 34.8, 121.7 (d, JP–C = 4.4 Hz), 128.5 (d, JP–C
=
Yield: 84%; mp 97–99 °C (Lit.4c 96–126 °C); E,E/Z,E ratio = 3.8:1.
11.7 Hz), 131.2 (d, JP–C = 9.5), 131.4 (d, JP–C = 101.0 Hz), 132.0 (d,
JP–C = 2.2 Hz), 133.6.
GC-MS (EI): m/z (%) = 316 (8) [M+], 216 (57), 215 (100), 201 (20),
IR (KBr): 840, 930, 1040, 1180, 1300, 1510, 1600, 1700, 2030,
2850, 2990, 3010 cm–1.
1H NMR (400 MHz, CDCl3): d (E,E-isomer) = 3.80 (s, 6 H), 6.62
(d, J = 15.4 Hz, 2 H), 6.67 (d, J = 15.4 Hz, 2 H), 6.85 (d,
J = 8.7 Hz, 4 H), 7.28 (d, J = 8.7 Hz, 4 H).
13C NMR (100 MHz, CDCl3): d (E,E-isomer) = 55.2, 114.1, 119.4,
127.1, 129.4, 130.4, 159.1.
77 (13).
Anal. Calcd for C18H21OPS: C, 68.33; H, 6.69. Found: C, 67.82; H,
7.21.
(Diphenylphosphinoyl)methyl(undec-1-enyl)sulfide (3h)
Yield: 62%; mp 81–83 °C; E/Z ratio = 4:1.
IR (KBr): 537, 694, 949, 1186 (P=O), 1437 cm–1.
GC-MS (EI): m/z (%) = 298 (100) [M+], 265 (25), 253 (25), 159
(26), 151 (58), 145 (39), 144 (28), 121 (54), 89 (29), 77 (35).
1H NMR (400 MHz, CDCl3): d (E-isomer) = 0.88 (t, J = 7.3 Hz,
Bis(4-chlorostyryl)sulfide (4d)
3 H), 1.20–1.32 (m, 14 H), 1.92–1.98 (m, 2 H), 3.40 (d, JP–H
=
Yield: 81%; mp 95–97 °C (Lit.4c 96–108 °C); E,E/Z,E ratio = 3.3:1.
8.8 Hz, 2 H), 5.65 (dt, J = 14.9, 7.3 Hz, 1 H), 5.89 (d, J = 14.9 Hz,
1 H), 7.45–7.56 (m, 6 H), 7.77–7.82 (m, 4 H).
IR (KBr): 508, 784, 796, 840, 933, 1012, 1093, 1401, 1488, 1557,
1587 cm–1.
1H NMR (400 MHz, CDCl3): d (E,E-isomer) = 6.63 (d, J = 15.6 Hz,
2 H), 6.82 (d, J = 15.6 Hz, 2 H), 7.26–7.34 (m, 8 H).
13C NMR (100 MHz, CDCl3): d (E,E-isomer) = 122.5, 127.0, 127.1,
128.9, 129.4, 134.9.
13C NMR (100 MHz, CDCl3): d (E-isomer) = 14.0, 22.5, 28.8, 28.9,
29.2, 29.3, 29.4, 31.6 (d, JP–C = 69.5 Hz), 31.8, 32.7, 121.4 (d, JP–C
=
3.7 Hz), 128.5 (d, JP–C = 11.7 Hz), 131.2 (d, JP–C = 9.5), 131.5 (d,
JP–C = 101.0 Hz), 132.0 (d, JP–C = 2.9 Hz), 133.9.
GC-MS (EI): m/z (%) = 400 (19) [M+], 337 (56), 277 (63), 250 (45),
GC-MS (EI): m/z (%) = 306 (87) [M+], 271 (23), 238 (45), 202 (39),
155 (100), 134 (75), 115 (88), 75 (75), 51 (39).
204 (100), 146 (30), 72 (60), 44 (97).
Anal. Calcd for C24H33OPS: C, 71.96; H, 8.30. Found: C, 71.55; H,
7.76.
Dipent-1-enylsulfide (4e)
Yield: 44%; oil; E,E/Z,E ratio = 1.3:1.
IR (neat): 694, 732, 964, 1172, 1575 cm–1.
Symmetrically Substituted Divinyl Sulfides 4a–f; General Pro-
cedure
1H NMR (400 MHz, CDCl3): d (E,E-isomer) = 0.90 (t, J = 7.3 Hz,
6 H), 1.36–1.47 (m, 4 H), 2.04–2.14 (m, 4 H), 5.73 (dt, J = 14.9,
7.3 Hz, 2 H), 5.97 (dt, J = 14.9, 1.5 Hz, 2 H).
13C NMR (100 MHz, CDCl3): d (both isomers) = 13.5, 13.5, 13.7,
22.1, 22.3, 22.4, 31.1, 35.1, 35.1, 121.1, 121.7, 123.0, 130.7, 131.7,
132.9.
NaH (dry 95%; 51 mg, 2 mmol) was added to a solution of
bis[(diphenylphosphinoyl)methyl]sulfide (231 mg, 0.5 mmol) in
THF (10 mL) at r.t. After 20 min, the appropriate carbonyl com-
pound (1.5 mmol) was added and the reaction was stirred for 3–4 h
(see Table). Sat. aq NH4Cl (20 mL) was added, the mixture was ex-
tracted with EtOAc (2 × 20 mL) and the organic layer was dried
(MgSO4), filtered and concentrated under reduced pressure. The
residue was purified by column chromatography eluting with hex-
anes.
GC-MS (EI): m/z (%) = 170 (89) [M+], 141 (60), 113 (23), 99 (70),
85 (100), 79 (57), 67 (58), 65 (62), 55 (55).
Bis(styryl)sulfide (4a)6
Diundec-1-enylsulfide (4f)
Yield: 38%; oil; E,E/Z,E ratio = 1.2:1.
Yield: 85%; mp 40–42 °C (Lit.11l 42–43 °C); E,E/Z,E ratio = 3.2:1.
IR (neat): 721, 938, 1465, 1605, 2924 cm–1.
IR (KBr): 942, 1444, 1567, 1595 cm–1.
1H NMR (400 MHz, CDCl3): d (E,E-isomer) = 0.90 (t, J = 7.3 Hz,
6 H), 1.23–1.32 (m, 28 H), 2.04–2.14 (m, 4 H), 5.73 (dt, J = 14.9,
7.3 Hz, 2 H), 5.97 (dt, J = 14.9, 1.5 Hz, 2 H).
13C NMR (100 MHz, CDCl3): d (both isomers) = 14.1, 22.7, 29.0,
29.1, 29.1, 29.2, 29.2, 29.3, 29.5, 29.6, 121.0, 121.6, 122.8, 131.0,
131.9, 133.2.
1H NMR (400 MHz, CDCl3): d (E,E-isomer) = 6.68 (d, J = 15.6 Hz,
2 H), 6.85 (d, J = 15.6 Hz, 2 H), 7.20–7.39 (m, 10 H).
13C NMR (100 MHz, CDCl3): d (E,E-isomer) = 121.7, 125.9, 127.5,
128.6, 130.6, 136.4.
GC-MS (EI): m/z (%) = 238 (100) [M+], 134 (32), 129 (33), 128
(40), 121 (77), 116 (56), 115 (85), 91 (74), 77 (85), 65 (32), 51 (69),
45 (33).
GC-MS (EI): m/z (%) = 338 (2) [M+], 335 (98), 334 (36), 222 (20),
110 (28), 96 (100), 95 (58), 82 (73), 42 (85).
Bis(4-methylstyryl)sulfide (4b)
Yield: 82%; mp 108–114 °C; E,E/Z,E ratio = 6:1.
Anal. Calcd for C22H42S: C, 78.03; H, 12.50. Found: C, 78.13; H,
12.41.
IR (KBr): 690, 780, 810, 953, 1090, 1200, 1360, 1495, 1509, 1602,
1904, 3001, 3005 cm–1.
1H NMR (400 MHz, CDCl3): d (E,E-isomer) = 2.33 (s, 6 H), 6.66
(d, J = 15.4 Hz, 2 H), 6.78 (d, J = 15.4 Hz, 2 H), 7.12 (d,
J = 8.0 Hz, 4 H), 7.24 (d, J = 8.0 Hz, 4 H).
13C NMR (100 MHz, CDCl3): d (E,E-isomer) = 21.1, 120.8, 125.8,
129.3, 130.6, 133.8, 137.3.
GC-MS (EI): m/z (%) = 266 (100) [M+], 251 (31), 233 (31), 218
(40), 143 (43), 142 (37), 135 (84), 134 (34), 130 (38), 129 (74), 128
(45), 115 (83), 105 (43), 91 (60), 65 (46), 45 (30).
Symmetrically Substituted Divinyl Sulfides 4g–j; General Pro-
cedure
NaH (dry 95%; 51 mg, 2 mmol) was added to a solution of
bis[(diphenylphosphinoyl)methyl]sulfide (231 mg, 0.5 mmol) in
THF (10 mL) at r.t. [for the preparation of 4j, HMPA (0.1 equiv)
was added to the reaction medium]. After 20 min, the appropriate
carbonyl compound (1.5 mmol) was added and the reaction was
stirred for 24 h at 60 °C (oil bath temperature). The reaction was
cooled to r.t., sat. aq NH4Cl (20 mL) was added and the mixture was
extracted with EtOAc (2 × 20 mL). The organic layer was dried
(MgSO4), filtered, and concentrated under reduced pressure. The
Synthesis 2011, No. 8, 1233–1242 © Thieme Stuttgart · New York

1240
C. C. Silveira et al.
PAPER
residue was purified by column chromatography eluting with hex-
anes.
EtOAc (2 × 20 mL), and the organic layer was dried (MgSO4), fil-
tered and concentrated under reduced pressure. The residue was pu-
rified by column chromatography, eluting with hexanes.
Bis(cyclohexylidenemethyl)sulfide (4g)11f
Yield: 69%; oil.
IR (neat): 722, 803, 864, 995, 1320, 1383, 1451, 3947 cm–1.
1H NMR (200 MHz, CDCl3): d = 1.53 (s, 12 H), 2.14–2.23 (m, 8 H),
5.65 (s, 2 H).
13C NMR (50 MHz, CDCl3): d = 26.4, 26.9, 28.1, 30.2, 36.2, 114.7,
141.1.
GC-MS (EI): m/z (%) = 222 (84) [M+], 139 (100), 126 (58), 97 (48),
93 (80), 81 (43), 77 (52), 65 (34), 55 (70), 53 (47), 45 (51).
[(4-tert-Butylcyclohexylidene)methyl](4-methoxystyryl)sulfide
(5a)6
Yield: 78%; mp 67–69 °C; E/Z ratio = 12:1.
IR (KBr): 1255, 1462, 1568, 1606 cm–1.
1H NMR (100 MHz, CDCl3): d (E-isomer) = 0.86 (s, 9 H), 1.00–
1.27 (m, 3 H), 1.75–1.92 (m, 3 H), 2.05–2.18 (m, 1 H), 2.36–2.46
(m, 1 H), 2.79–2.89 (m, 1 H), 3.79 (s, 3 H), 5.80 (s, 1 H), 6.43 (d,
J = 15.3 Hz, 1 H), 6.59 (d, J = 15.3 Hz, 1 H), 6.83 (d, J = 8.9 Hz,
2 H), 6.59 (d, J = 8.9 Hz, 2 H).
13C NMR (100 MHz, CDCl3): d (E-isomer) = 27.5, 27.9, 28.9, 30.3,
32.4, 36.4, 47.9, 55.2, 111.1, 114.0, 121.8, 126.6, 126.7, 129.9,
146.1, 158.6.
GC-MS (EI): m/z (%) = 316 (81) [M+], 217 (25), 195 (77), 147 (25),
134 (82), 122 (19), 121 (100), 97 (30), 91 (19), 57 (60), 44 (27), 43
(35), 41 (37).
Bis[(4-methylcyclohexylidene)methyl]sulfide (4h)
Yield: 72%; oil; obtained as a ~1:1 mixture of diastereoisomers.
IR (neat): 750, 806, 844, 951, 1011, 1234, 1295, 1450, 2919 cm–1.
1H NMR (400 MHz, CDCl3): d = 0.89 (d, J = 6.7 Hz, 6 H), 0.94–
1.05 (m, 4 H), 1.49–1.55 (m, 2 H), 1.71–1.74 (m, 4 H), 1.78–1.86
(m, 2 H), 2.02–2.10 (m, 2 H), 2.24–2.27 (m, 2 H), 2.65–2.69 (m,
2 H), 5.66 (s, 2 H).
13C NMR (100 MHz, CDCl3): d = 21.8, 29.5, 32.3, 35.0, 35.5, 36.1,
114.55/114.55, 140.91/140.95.
Anal. Calcd for C20H28OS: C, 75.90; H, 8.92. Found: C, 75.84; H,
8.99.
[(4-tert-Butylcyclohexylidene)methyl](4-methylstyryl)sulfide
(5b)
Yield: 85%; mp 47–49 °C; E/Z ratio = 10:1.
IR (KBr): 779, 812, 932, 1342 cm–1.
1H NMR (100 MHz, CDCl3): d (E-isomer) = 0.86 (s, 9 H), 1.00–
1.22 (m, 3 H), 1.77–1.90 (m, 3 H), 2.07–2.15 (m, 1 H), 2.30 (s,
3 H), 2.39–2.45 (m, 1 H), 2.84–2.89 (m, 1 H), 5.81 (s, 1 H), 6.44 (d,
J = 15.4 Hz, 1 H), 6.67 (d, J = 15.4 Hz, 1 H), 7.08 (d, J = 8.2 Hz,
2 H), 7.18 (d, J = 8.2 Hz, 2 H).
GC-MS (EI): m/z (%) = 250 (85) [M+], 153 (95), 140 (27), 107
(100), 93 (45), 91 (47), 81 (49), 77 (32), 67 (85), 55 (83).
Anal. Calcd for C16H26S: C, 76.73; H, 10.46. Found: C, 76.64; H,
10.04.
Bis[(4-tert-butylcyclohexylidene)methyl]sulfide (4i)
Yield: 78%; mp 69–71 °C; obtained as a ~1:1 mixture of diaste-
reomers.
13C NMR (100 MHz, CDCl3): d (E-isomer) = 21.1, 27.6, 27.9, 28.9,
30.3, 32.4, 36.4, 47.9, 110.8, 123.2, 125.4, 126.7, 129.3, 134.3,
136.5, 146.5.
GC-MS (EI): m/z (%) = 300 (52) [M]+, 201 (33), 195 (49), 134 (21),
118 (42), 105 (50), 97 (26), 91 (29), 79 (28), 57 (100).
IR (KBr): 727, 819, 988, 1239, 1336, 1444, 1480, 1618, 2831, 2960
cm–1.
1H NMR (400 MHz, CDCl3): d = 0.84 (s, 18 H), 0.99–1.19 (m, 6 H),
1.73–1.85 (m, 6 H), 2.00–2.08 (m, 2 H), 2.29–2.34 (m, 2 H), 2.70–
2.80 (m, 2 H), 5.65 (s, 2 H).
13C NMR (100 MHz, CDCl3): d = 27.6, 27.7, 28.8, 30.1, 32.4, 36.2,
48.0, 114.21/114.23, 141.37/141.37.
Anal. Calcd for C20H28S: C, 79.94; H, 9.39. Found: C, 80.00; H,
9.68.
GC-MS (EI): m/z (%) = 334 (29) [M+], 195 (26), 97 (19), 95 (16),
93 (23), 91 (20), 81 (19), 69 (16), 67 (17), 57 (100), 55 (31).
[(4-tert-Butylcyclohexylidene)methyl](4-chlorostyryl)sulfide
(5c)
Yield: 85%; mp 40–42 °C; E/Z ratio = 4:1.
IR (KBr): 806, 1089, 1364, 1488, 1595 cm–1.
Anal. Calcd for C22H38S: C, 78.97; H, 11.45. Found: C, 79.29; H,
11.44.
1H NMR (200 MHz, CDCl3): d (E-isomer) = 0.86 (s, 9 H), 0.98–
1.21 (m, 3 H), 1.83–1.92 (m, 3 H), 2.06–2.19 (m, 1 H), 2.40–2.49
(m, 1 H), 2.82–2.90 (m, 1 H), 5.80 (s, 1 H), 6.38 (d, J = 14.8 Hz,
1 H), 6.73 (d, J = 14.8 Hz, 1 H), 7.16–7.28 (m, 4 H).
Bis(2,2-diphenylvinyl)sulfide (4j)
Yield: 69%; mp 108–110 °C (Lit.14 116–117 °C).
IR (KBr): 758, 824, 1019, 1152, 1336, 1444, 1495, 1582, 1951,
3021, 3047 cm–1.
13C NMR (100 MHz, CDCl3): d (E-isomer) = 27.6, 28.0, 28.9, 30.4,
32.4, 36.5, 47.9, 110.1, 124.8, 125.6, 126.6, 128.7, 132.2, 135.6,
147.6.
GC-MS (EI): m/z (%) = 320 (28) [M]+, 195 (26), 134 (18), 125 (42),
97 (20), 57 (100), 41 (72).
1H NMR (400 MHz, CDCl3): d = 6.80 (s, 2 H), 7.19–7.36 (m, 20 H).
13C NMR (100 MHz, CDCl3): d = 124.5, 127.1, 127.2, 127.8, 128.2,
128.3, 129.6, 138.9, 139.9, 141.6.
GC-MS (EI): m/z (%) = 390 (57) [M+], 223 (21), 210 (24), 199 (53),
192 (100), 191 (49), 179 (22), 178 (85), 176 (20), 167 (25), 165
(56), 152 (30), 121 (42), 77 (37), 51 (43).
Anal. Calcd for C19H25ClS: C, 71.11; H, 7.85. Found: C, 71.58; H,
7.43.
Preparation of Unsymmetrical Divinyl Sulfides 5a–f; General
Procedure
NaH (dry 95%; 25 mg, 1 mmol) was added to a solution of (diphe-
nylphosphinoyl)methyl vinyl sulfide 3d (199 mg, 0.5 mmol) in THF
(15 mL) at r.t. After 20 min, the appropriate carbonyl compound
(0.75 mmol) was added and the reaction was stirred for 3, 4, or 12 h.
Sat. aq NH4Cl (20 mL) was added, the mixture was extracted with
5-{2-[(4-tert-Butylcyclohexylidene)methylthio]vinyl}ben-
zo[d][1,3]dioxole (5d)
Yield: 82%; mp 48–50 °C; E/Z ratio = 10:1.
IR (KBr): 947, 1101, 1249, 1488, 1502 cm–1.
1H NMR (400 MHz, CDCl3): d (E-isomer) = 0.86 (s, 9 H), 0.99–
1.22 (m, 3 H), 1.77–1.90 (m, 3 H), 2.07–2.14 (m, 1 H), 2.40–2.44
Synthesis 2011, No. 8, 1233–1242 © Thieme Stuttgart · New York

PAPER
Synthesis of Vinyl and Divinyl Sulfides
IR (neat): 804, 988, 1290, 1365, 1441 cm–1.
1H NMR (400 MHz, CDCl3): d = 0.84 (s, 9 H), 0.89 (d, J = 6.6 Hz,
3 H), 0.94–1.18 (m, 5 H), 1.46–1.59 (m, 1 H), 1.72–1.77 (m, 3 H),
1.80–1.87 (m, 3 H), 2.00–2.10 (m, 2 H), 2.22–2.34 (m, 2 H), 2.65–
2.69 (m, 1 H), 2.73–2.78 (m, 1 H), 5.65 (s, 1 H), 5.67 (s, 1 H).
13C NMR (100 MHz, CDCl3): d = 21.9/21.9, 27.6/27.6 (3C), 27.67/
27.68 (2C), 28.8/28.8, 29.6/30.1, 32.3/32.4 (2C), 35.1/35.6 (2C),
36.19/36.23 (2C), 47.9/47.9, 114.19/114.21, 114.67/114.68,
140.93/140.97, 141.32/141.37.
1241
(m, 1 H), 2.83–2.88 (m, 1 H), 5.79 (s, 1 H), 5.91 (s, 2 H), 6.38 (d,
J = 15.4 Hz, 1 H), 6.55 (d, J = 15.4 Hz, 1 H), 6.71 (s, 2 H), 6.82 (s,
1 H).
13C NMR (100 MHz, CDCl3): d (E-isomer) = 27.6, 27.9, 28.9, 30.3,
32.4, 36.4, 47.9, 101.0, 105.0, 108.3, 110.8, 120.0, 122.5, 126.6,
131.6, 146.6, 148.0.
GC-MS (EI): m/z (%) = 330 (60) [M]+, 195 (68), 148 (85), 135
(100), 121 (28), 97 (39), 77 (32), 57 (97), 41 (76).
Anal. Calcd for C20H26O2S: C, 72.69; H, 7.93. Found: C, 72.69; H,
7.81.
GC-MS (EI): m/z (%) = 292 (4) [M]+, 290 (37), 289 (100), 288 (49),
193 (20), 106 (34), 96 (23), 57 (34).
[(4-tert-Butylcyclohexylidene)methyl](pent-1-enyl)sulfide (5e)
Yield: 51%; oil; E/Z ratio = 1:1.
IR (neat): 940, 987, 1365, 1442, 1608 cm–1.
Anal. Calcd for C19H32S: C, 78.01; H, 11.03. Found: C, 78.39; H,
10.61.
[(4-tert-Butylcyclohexylidene)methyl]-(2,2-diphenylvinyl)sul-
fide (5h)
Yield: 54%; mp 88–90 °C.
IR (KBr): 754, 1364, 1441, 1493, 1584 cm–1.
1H NMR (400 MHz, CDCl3): d = 0.83 (s, 9 H), 0.94–1.18 (m, 3 H),
1.70–1.78 (m, 1 H), 1.79–1.87 (m, 2 H), 2.01–2.08 (m, 1 H), 2.32–
2.37 (m, 1 H), 2.69–2.74 (m, 1 H), 5.84 (s, 1 H), 6.66 (s, 1 H), 7.17–
7.32 (m, 8 H), 7.36–7.40 (m, 2 H).
13C NMR (100 MHz, CDCl3): d = 27.6, 27.7, 28.8, 30.2, 32.4, 36.2,
47.9, 113.7, 125.6, 126.8, 126.9, 127.5, 128.2, 128.3, 129.7, 138.1,
139.4, 141.7, 143.4.
1H NMR (400 MHz, CDCl3): d (both isomers) = 0.85 (s, 18 H), 0.90
(t, J = 7.3 Hz, 3 H), 0.93 (t, J = 7.3 Hz, 3 H), 0.96–1.20 (m, 6 H),
1.36–1.48 (m, 4 H), 1.73–1.89 (m, 6 H), 2.01–2.13 (m, 6 H), 2.30–
2.39 (m, 2 H), 2.73–2.82 (m, 2 H), 5.56 (dt, J = 9.0, 7.3 Hz, 1 H),
5.64 (dt, J = 14.9, 7.3 Hz, 1 H), 5.67–5.69 (m, 2 H), 5.96 (dt, J =
14.9, 1.2 Hz, 1 H), 5.99 (dt, J = 9.0, 1.5 Hz, 1 H).
13C NMR (100 MHz, CDCl3): d (both isomers) = 13.6, 13.8, 22.2,
22.5, 27.6, 27.7, 27.8, 28.8, 28.9, 30.2, 30.2, 31.2, 32.4, 35.1, 36.2,
36.3, 47.9, 48.0, 112.1, 113.4, 122.4, 124.6, 128.9, 130.3, 142.2,
144.2.
GC-MS (EI): m/z (%) = 252 (2) [M]+, 250 (27), 249 (100), 248 (34),
193 (31), 134 (18), 96 (22), 92 (28), 80 (20), 56 (61).
GC-MS (EI): m/z (%) = 362 (4) [M]+, 359 (41), 358 (100), 357 (54),
Anal. Calcd for C16H28S: C, 76.12; H, 11.18. Found: C, 76.41; H,
10.72.
178 (43), 176 (35), 165 (39), 57 (30).
Anal. Calcd for C25H30S: C, 82.82; H, 8.34. Found: C, 82.81; H,
8.36.
[(4-tert-Butylcyclohexylidene)methyl](undec-1-enyl)sulfide (5f)
Yield: 60%; oil; E/Z ratio = 1:1.
IR (neat): 940, 987, 1365, 1442, 1608 cm–1.
Acknowledgment
1H NMR (400 MHz, CDCl3): d (both isomers) = 0.85 (s, 18 H), 0.88
(t, J = 6.6 Hz, 6 H), 0.95–1.20 (m, 6 H), 1.20–1.42 (m, 28 H), 1.73–
1.88 (m, 6 H), 2.00–2.14 (m, 6 H), 2.30–2.39 (m, 2 H), 2.74–2.82
(m, 2 H), 5.55 (dt, J = 9.3, 7.3 Hz, 1 H), 5.64 (dt, J = 14.9, 7.3 Hz,
1 H), 5.67–5.69 (m, 2 H), 5.95 (dt, J = 14.9, 1.2 Hz, 1 H), 5.97 (dt,
J = 9.3, 1.5 Hz, 1 H).
13C NMR (100 MHz, CDCl3): d (both isomers) = 14.1, 22.7, 27.6,
27.7, 27.8, 28.7, 28.8, 28.9, 29.0, 29.1, 29.1, 29.2, 29.3, 29.3, 29.4,
29.5, 29.5, 29.6, 30.1, 30.2, 31.8, 32.4, 33.1, 36.2, 36.3, 47.9, 48.0,
112.2, 113.5, 122.2, 124.4, 129.1, 130.5, 142.1, 144.0.
The authors thank MCT/CNPq, FAPERGS and CAPES for finan-
cial support. T.S.K. also thanks CONICET.
References
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Unsymmetrical Divinyl Sulfides 5g–h; General Procedure
NaH (dry 95%; 25 mg, 1 mmol) was added to a solution of (diphe-
nylphosphinoyl)methyl vinyl sulfide 3d (199 mg, 0.5 mmol) in THF
(15 mL) at r.t. After 20 min, the appropriate carbonyl compound
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Synthesis 2011, No. 8, 1233–1242 © Thieme Stuttgart · New York

1242
C. C. Silveira et al.
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