One-pot preparation of arylethynyl sulfides and bis(arylethynyl) sulfides

Article abstract of DOI:10.1002/ejoc.201201422

An efficient preparation for arylethynyl sulfides 1 and bis(arylethynyl) sulfides 2 has been accomplished through a one-pot, three-step strategy that starts from arylethanonyl sulfides and bis(arylethanonyl) sulfides, respectively, without the use of various terminal arylacetylenes as substrates. When lithium hexamethyldisilazane (LHMDS), ClP(O)(OEt)₂, and LHMDS were sequentially added to a tetrahydrofuran solution of different substrates [arylethanonyl sulfides or bis(arylethanonyl) sulfides], 1 or 2 were obtained in moderate to good yields. The reaction procedure involves the formation of an enol phosphate and a subsequent base-induced elimination. An efficient preparation of arylethynyl sulfides 1 and bis(arylethynyl) sulfides 2 has been accomplished by a one-pot, three-step strategy that starts from arylethanonyl sulfides and bis(arylethanonyl) sulfides, respectively, to give 1 and 2 in moderate to good yields. The reaction mechanism involves the formation of an enol phosphate that undergoes a subsequent base-induced elimination. Copyright

Full text of DOI:10.1002/ejoc.201201422

FULL PAPER
DOI: 10.1002/ejoc.201201422
One-Pot Preparation of Arylethynyl Sulfides and Bis(arylethynyl) Sulfides
Qiong Su,[a] Zi-Jian Zhao,[a] Feng Xu,[a] Peng-Cai Lou,[a] Kai Zhang,[a] De-Xun Xie,[a]
Lei Shi,[a] Qing-Yun Cai,*[a] Zhi-Hong Peng,*[a] and De-Lie An*[a]
Keywords: Synthetic methods / Alkynes / Sulfur
An efficient preparation for arylethynyl sulfides 1 and bis-
(arylethynyl) sulfides 2 has been accomplished through a
one-pot, three-step strategy that starts from arylethanonyl
sulfides and bis(arylethanonyl) sulfides, respectively, without
the use of various terminal arylacetylenes as substrates.
When lithium hexamethyldisilazane (LHMDS), ClP(O)(OEt)
2, and LHMDS were sequentially added to a tetrahydrofuran
solution of different substrates [arylethanonyl sulfides or bis-
(arylethanonyl) sulfides], 1 or 2 were obtained in moderate
to good yields. The reaction procedure involves the formation
of an enol phosphate and a subsequent base-induced elimi-
nation.
well as number of methylthio groups (SMe), were also ap-
plied to exploit their unique optical and electrical proper-
ties.[4] To further compare the behavior of different rigid
molecules as interparticle linkages, it is necessary to investi-
gate a wide range of various multidentate compounds.
Hence, we need a generally applicable way to prepare the
terminal building block Ar–CϵC–SR. The most fruitful
methodologies involve the use of arylacetylenes for the
preparation of arylethynyl sulfides.[5,6d,6e] Although several
other methodologies have been reported, their protocols re-
quire either uncommon substrates[6] such as special thia-
diazoles,[6a] phosphorus ylides,[6b] phosphanyldithioate,[6d]
and so forth or suffer from stringent experimental condi-
tions.[6b] We have also demonstrated a convenient method-
ology for the preparation of arylethynyl methyl sulfides,
which starts from methylthiomethyl phenyl sulfone
(MP-S)[7] and an aromatic aldehyde in a one-pot protocol.[8]
Unfortunately, this method is restricted in its applicability
and is limited to the specific substrate MP-S. Thus, it is only
suitable for the synthesis of methylthio derivatives (Ar–
CϵC–SCH3). Very recently, a report by Pan et al. described
a new methodology, which uses 1,1-dibromo-1-alkenes, for
a transition-metal-free-catalyzed C–S coupling of vinyl di-
bromide with thiophenols.[9,10]
In addition, bis(1-alkynyl) sulfides (R–CϵC–S–CϵC–R)
are an interesting class of molecules that have garnered
much attention in synthetic chemistry and photochemical
studies on account of their strikingly high reactivity as well
as special structural features. For example, Brandsma et al.
showed that the nucleophilic addition to bis(1-alkynyl)
sulfide by chalcogenide reagents could afford six-membered
heterocyclic products.[11] Matzger and co-workers described
a cycloaromatization through the photoirradiation of
bis(phenylethynyl) sulfide to produce a 3,4-disubstituted
thiophene.[12] Unfortunately, there are very few acceptable
Introduction
Because of their unique structural features as well as op-
tical and electronic properties, acetylene compounds have
long been an attractive area of research.[1] The use of multi-
dentate sulfur-containing molecules as interparticle linkages
has led to an increasing interest in the assembly of gold
nanoparticles.[2] Although a fundamental understanding of
controlling interparticle spatial properties remains very lim-
ited, from the perspective of morphology control, rigid mo-
lecules could serve as ideal model systems for defining inter-
particle structures because of their well-defined spatial ori-
entation properties. However, much less attention has been
paid to rigid molecular mediators in comparison to the ex-
tensive studies on the use of aliphatic derivatives with flexi-
ble frameworks.[3] Recently, we reported on the viability of
rigid molecules as interparticle linkages through the coordi-
nation of some rigid multimethylthio arylethynyl molecules
to gold surfaces.[4] These molecules exhibited some charac-
teristics for controlling the sizes of nanoclusters and showed
a reversible behavior of assembly/disassembly.
Arylethynyl sulfides are very important intermediates in
organic synthesis and can be used as versatile building
blocks for a variety of chemical purposes. In our studies on
the assembly of gold nanoparticles mediated by functional
materials, various arylethynyl compounds, which are well-
defined in terms of structural rigidity, size, and shape as
[a] State Key Laboratory of Chemo/Biosensing and Chemometrics,
College of Chemistry and Chemical Engineering, Hunan
University,
Changsha 410082, China
Fax: +86-731-88827944
E-mail: deliean@hnu.edu.cn
qycai0001@hnu.edu.cn
pzh7251@hnu.edu.cn
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201201422.
Eur. J. Org. Chem. 2013, 1551–1557
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Q.-Y. Cai, Z.-H. Peng, D.-L. An et al.
FULL PAPER
methods to prepare bis(1-alkynyl) sulfides thus far, and, in Table 1. Preparation of arylethynyl sulfides 1.[a]
most cases, a successful protocol must use alkynyl com-
pounds as substrates.[13]
Herein, we wish to report a new and effective one-pot
strategy for the preparation of arylethynyl sulfides 1 and
bis(arylethynyl) sulfides 2 from arylethanonyl sulfides and
bis(arylethanonyl) sulfides, respectively, without the use of
Entry Ar
R
Product
Yield [%][b]
terminal arylacetylenes.
1
2
3
4
5
6
7
8
C6H5
Me
Me
Me
Me
Me
Me
Me
Me
1a
1b
1c
1d
1e
1f
1g
1h
1i
77
72
83
79
82
78
77
71
77
70
74
78
75
87
83
87
75
81
74
82
85
78
74
86
75
4-MeOC6H4
2,5-(MeO)2C6H3
4-MeC6H4
4-IC6H4
4-BrC6H4
4-ClC6H4
Results and Discussion
First, we employed arylethanonyl sulfides, which were
conveniently obtained by the substitution reaction of the
corresponding sulfide reagent MeSNa, EtSNa, or PhSNa
with 2-bromo-1-arylethanone (see Supporting Infor-
mation), to prepare the arylethynyl sulfides. As shown in
Table 1, by using these substrates, the one-pot, three-step
method afforded the desired products 1 in satisfactory
yields. A typical procedure (for 1a) began with a solution
of phenylethanonyl methyl sulfide in tetrahydrofuran
(THF), and to this were sequentially added lithium hexa-
methyldisilazane (LHMDS), ClP(O)(OEt)2, and LHMDS. 18
After an usual workup, the crude mixture was subjected to
silica gel chromatography with petroleum ether as the elu-
ent to give product 1a in 77% yield.
2-naphthyl
9
6-MeO-2-naphthyl Me
3-NO2C6H4 Me
3,4-(OCH2O)C6H3 Me
10
11
12
13
14
15
16
17
1j
1k
1l
C6H5
Et
Et
Et
Et
Et
Et
Et
Et
4-MeOC6H4
2,5-(MeO)2C6H3
4-MeC6H4
4-IC6H4
4-BrC6H4
4-ClC6H4
2-naphthyl
6-MeO-2-naphthyl Et
3-NO2C6H4 Et
3,4-(OCH2O)C6H3 Et
2,5-(MeO)2C6H3
4-IC6H4
1m
1n
1o
1p
1q
1r
1s
1t
1u
1v
1w
1x
1y
19
20
21
22
23
24
25
The other arylethynyl sulfides 1b–1y were prepared in a
similar manner that started from the corresponding aryl-
ethanonyl sulfides. This one-pot reaction is quite simple
and does not require a tedious separation of intermediates.
Moreover, various groups on the aromatic ring (on the Ar
group) such as methoxy, methyl, chloro, iodo, and nitro
were well tolerated under the reaction conditions. Note that
iodo-substituted derivatives 1e, 1p, and 1x are pivotal build-
ing blocks for constructing rigid multidentate molecules,
and we have used 1e for this purpose.[4] In addition, both
aliphatic (Me, Et) and aryl (Ph) groups are effective as sub-
stitutes for the R group.
Ph
Ph
Ph
4-ClC6H4
[a] Reagents and conditions: (i) LHMDS (1.0 equiv.), THF, –78 °C,
30 min; (ii) ClP(O)(OEt)2 (1.2 equiv.), –78 °, then room temp.,
30 min; (iii) LHMDS (2.5 equiv.), –78 °C, 1 h. [b] Isolated yield.
Table 2. Preparation of symmetrical bis(arylethynyl) sulfides 2.[a]
To verify whether this one-pot, three-step protocol is ver-
satile, we extended it to the preparation of symmetrical
bis(arylethynyl) sulfides. Analogously, the bis(aryl-
ethanonyl) sulfides, which were used as substrates, were pre-
pared from 2-bromo-1-arylethanone and Na2S (see Sup-
porting Information). The sequential addition of LHMDS,
ClP(O)(OEt)2, and LHMDS to a THF solution of the
bis(arylethanonyl) sulfides, followed by aqueous workup
and chromatography, gave the desired compounds 2 in rea-
sonable isolated yields (see Table 2). Although the yield of
2 was somewhat lower than that of 1, this protocol provides
an entirely new method for the preparation of bis(aryl-
ethynyl) sulfides without using various terminal arylacetyl-
enes.
Entry
Ar
Product
Yield [%][b]
1
2
3
4
5
6
7
8
C6H5
2a
2b
2c
2d
2e
2f
65
64
63
76
74
70
72
71
4-MeOC6H4
2,5-(MeO)2C6H3
4-MeC6H4
4-IC6H4
4-ClC6H4
2-naphthyl
6-MeO-2-naphthyl
2g
2h
[a] Reagents and conditions: (i) LHMDS (2.0 equiv.), THF, –78 °C,
30 min; (ii) ClP(O)(OEt)2 (2.2 equiv.), –78 °C then room temp.,
30 min; (iii) LHMDS (5.0 equiv.), –78 °C, 1 h. [b] Isolated yield.
lie in a common plane. The bond lengths of C-1–C-2 and
The structure of 2h was unambiguously determined by C-13–C-14 are characteristic of the CϵC bond. The bond
the X-ray crystal structure analysis (see Figure 1). The lengths of S-1–C-1 and S-1–C-13 are shorter than general
ORTEP drawing presents a molecular structure of the “V” C–S single bonds and longer than analogous C=S double
type, in which atoms S-1, C-1, and C-2 and S-1, C-13, and bonds,[14] which indicates a certain degree of conjugation
C-14 are arranged in two intersecting lines with a 103° in- between the lone pair on the sulfur atom and π electrons of
cluded angle, and the atoms S-1, C-1, C-2, C-13, and C-14 the CϵC bond.
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One-Pot Preparation of Ethynyl Sulfides
Scheme 1. A plausible reaction mechanism.
Figure 1. X-ray crystal structure of compound 2h. The selected
bond lengths [Å] and angles [°] are as follows: C-1–C-2, 1.193(3);
C-2–C-3, 1.435(3); C-13–C-14, 1.191(3); C-14–C-15, 1.438(3); S-1–
C-1, 1.679(2); S-1–C-13, 1.684(2); C-1–C-2–C-3, 176.2(2); C-2–C-
1–S-1, 174.44(19); C-13–C-14–C-15, 177.6(2); C-14–C-13–S-1,
172.26(19); C-1–S-1–C-13, 103.05(10).
Scheme 2. Formation of enol phosphate 3a and preparation of 1a
through intermediate 3a.
Furthermore, we investigated the elimination reaction of
enol phosphate intermediate 3a, which, upon treating a
THF solution of 3a with LHMDS (2.5 equiv.), occurred
smoothly to provide 1a in 91% yield. Therefore, on the ba-
sis of this evidence, we can conclude that the mechanism
involves the formation of an enol phosphate and a subse-
quent base-induced elimination.
A plausible mechanism for the formation of 1 is pro-
posed in Scheme 1 (A). Enolate 5 is generated in situ from
the reaction between arylethanonyl sulfide and LHMDS.
The nucleophilic attack of enolate 5 on ClP(O)(OEt)2 yields
enol phosphate 3, which then undergoes an elimination
upon treatment with LHMDS to give arylethynyl sulfide
1. Analogously, Scheme 1 (B) illustrates the process for the
formation of bis(arylethynyl) sulfide 2. Thus, dienolate 6,
which results from the treatment of bis(arylethanonyl) sulf-
ide with LHMDS, undergoes a nucleophilic attack on
ClP(O)(OEt)2 to give bis(enol phosphate) 4. The base-in-
duced elimination involving intermediate 4 with two leaving
groups affords product 2.
To obtain insight into the mechanism of this one-pot re-
action, we attempted to isolate key intermediate 3. A differ-
entiated two-step procedure (with phenylethanonyl methyl
sulfide as the substrate) was performed to prove the forma-
tion of enol phosphate 3. As expected, after the addition of
LHMDS and ClP(O)(OEt)2 and then quenching the reac-
tion mixture with a saturated NH4Cl solution, 3a was ob-
tained in 80% yield (see Scheme 2). The results from the 1H
and 31P NMR spectroscopic data reveal that 3a was formed
in a Z/E mixture (93:7). The minor isomer (δP = –5.33 ppm)
was speculated to have the E configuration because of the
greater steric hindrance between the substituents Ph and
SMe on the same side of the C=C bond. The Z configura-
tion was assigned to the major isomer (δP = –5.43 ppm) and
has been confirmed by a NOESY experiment (NOE be-
tween Ha and Hb was observed, see Supporting Infor-
mation for details).
Conclusions
In summary, although the preparation of alkynyl ethers
from α-alkoxy ketones has been demonstrated by Minehan
and co-workers,[15] our work is the first to disclose a
straightforward, one-pot method for the preparation of
arylethynyl sulfides and bis(arylethynyl) sulfides that starts
from arylethanonyl sulfides and bis(arylethanonyl) sulfides,
respectively. The mechanism was discussed and studied by
trapping and characterizing the enol phosphate intermedi-
ate as well by following its direct elimination. This method
is not only simple, but also allows for a wide range of sub-
strates to be used as precursors for the preparation of asym-
metrical and symmetrical arylethynyl sulfides.
Experimental Section
General Methods: All reactions were carried out under nitrogen
with freshly distilled solvents. THF was distilled from sodium/
benzophenone. The solution of LHMDS in THF/ethylbenzene and
ClP(O)(OEt)2 were purchased from J&Kchemica. All aryl-
ethanonyl sulfides and bis(arylethanonyl) sulfides, which were used
as substrates, were prepared according to the procedures given in
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Q.-Y. Cai, Z.-H. Peng, D.-L. An et al.
FULL PAPER
the Supporting Information. Flash column chromatography was
performed on 300–400 mesh silica gel. All melting points were mea-
sured with a Taike XT-4 micromelting point apparatus. The 1H and
13C NMR spectroscopic data were recorded with a Varian INOVA-
400 instrument. CDCl3, with TMS as the internal standard, was
used as the solvent for the NMR samples. The 31P NMR spectro-
scopic data was recorded with a Varian INOVA-400 instrument.
CDCl3 was used as the solvent with 85% H3PO4 as the internal
standard for the 31P NMR samples. Mass spectra were recorded
CH3), 2.79 (q, J = 7.2 Hz, 2 H, CH2), 3.79 (s, 3 H, OCH3), 6.82
(d, J = 9.2 Hz, 2 H, Ar), 7.37 (d, J = 8.8 Hz, 2 H, Ar) ppm. 13C
NMR (100 MHz, CDCl3): δ = 14.65 (CH3), 29.98 (CH2), 55.21
(OCH3), 77.17 (Cϵ), 93.17 (Cϵ), 113.86 (CH), 115.62 (C), 133.26
(CH), 159.51 (C) ppm. IR (neat): ν = 2964, 2928, 2869, 2836, 2166
˜
(CϵC), 1605, 1569, 1507, 1462, 1441, 1375, 1290, 1249, 1171, 1106,
1032, 968, 831, 778, 644, 587, 537 cm–1. MS (EI): m/z (%) = 192
(100) [M]+, 164 (94), 163 (85), 149 (68). HRMS (EI): calcd. for
C11H12OS 192.0603; found 192.0603.
with
a
SHIMAZU GC-17 QP-5000 or ThermoFinnigan
(2,5-Dimethoxyphenyl)ethynyl Ethyl Sulfide (1n): Pale yellow oil
(87% yield). H NMR (400 MHz, CDCl3): δ = 1.46 (t, J = 7.6 Hz,
MAT95XP. FTIR spectra were taken with a Nicolet 6700 FT-IR
spectrometer. The X-ray diffraction measurement on a single crys-
tal was carried out at 293(2) K with a Bruker SMART CCD area
detector with graphite monochromated Mo-Kα radiation (λ =
0.71073 Å).
1
3 H, CH3), 2.82 (q, J = 7.6 Hz, 2 H, CH2), 3.74 (s, 3 H, OCH3),
3.81 (s, 3 H, OCH3), 6.77–6.79 (m, 2 H, Ar), 6.92 (d, J = 2.8 Hz,
1 H, Ar) ppm. 13C NMR (100 MHz, CDCl3): δ = 14.57 (CH3),
30.01 (CH2), 55.66 (OCH3), 56.31 (OCH3), 83.14 (Cϵ), 89.60
(Cϵ), 111.92 (CH), 113.25 (C), 115.14 (CH), 117.81 (CH), 153.08
Typical One-Pot Procedure for the Preparation of Arylethynyl Sulf-
ides 1a–1y: LHMDS (1.0 m in THF/ethylbenzene, 1.8 mL) was
added to a solution of arylethanonyl sulfide (1.8 mmol) in THF
(15 mL) at –78 °C, and the mixture was stirred for 30 min. Then,
ClP(O)(OEt)2 (0.31 mL, 2.2 mmol) was added dropwise at –78 °C,
and the resulting mixture was warmed to room temperature and
stirred for 30 min. The reaction mixture was cooled to –78 °C and
then LHMDS (1.0 m in THF/ethylbenzene, 4.5 mL) was added. Af-
ter stirring at this temperature for 1 h, the reaction was quenched
with an aqueous NH4Cl solution. The mixture was extracted with
AcOEt (3ϫ30 mL). The organic layer was washed with brine, dried
with MgSO4, and filtered. The solvent was evaporated in vacuo,
and the residue was subjected to flash column chromatography (pe-
troleum ether) to give arylethynyl sulfide 1.
(C), 154.43 (C) ppm. IR (neat): ν = 2926, 2853, 2162 (CϵC), 1603,
˜
1577, 1498, 1463, 1308, 1229, 1045, 729 cm–1. MS (EI): m/z (%) =
222 (100) [M]+, 194 (23), 179 (68). HRMS (EI): calcd. for
C12H14O2S 222.0709; found 222.0706.
(4-Methylphenyl)ethynyl Ethyl Sulfide (1o): Colorless oil (83%
1
yield). H NMR (400 MHz, CDCl3): δ = 1.44 (t, J = 7.6 Hz, 3 H,
CH3), 2.32 (s, 3 H, CH3), 2.79 (q, J = 7.6 Hz, 2 H, CH2), 7.09 (d,
J = 8.0 Hz, 2 H, Ar), 7.31 (d, J = 8.4 Hz, 2 H, Ar) ppm. 13C NMR
(100 MHz, CDCl3): δ = 14.66 (CH3), 21.39 (CH3), 29.91 (CH2),
78.11 (Cϵ), 93.46 (Cϵ), 120.39 (C), 128.96 (CH), 131.39 (CH),
138.09 (C) ppm. IR (neat): ν = 2966, 2926, 2869, 2166 (CϵC),
˜
1606, 1506, 1447, 1258, 815 cm–1. MS (EI): m/z (%) = 176 (76)
[M]+, 148 (100), 147 (70), 103 (22). HRMS (EI): calcd. for C11H12S
176.0654; found 176.0654.
(4-Chlorophenyl)ethynyl Methyl Sulfide (1g): Colorless oil (77%
1
yield). H NMR (400 MHz, CDCl3): δ = 2.46 (s, 3 H, SCH3), 7.25
(4-Iodophenyl)ethynyl Ethyl Sulfide (1p): Yellow oil (87% yield). 1H
NMR (400 MHz, CDCl3): δ = 1.44 (t, J = 7.6 Hz, 3 H, CH3), 2.82
(q, J = 7.6 Hz, 2 H, CH2), 7.12 (d, J = 8.4 Hz, 2 H, Ar), 7.62 (d,
J = 8.4 Hz, 2 H, Ar) ppm. 13C NMR (100 MHz, CDCl3): δ = 14.73
(CH3), 29.94 (CH2), 81.14 (Cϵ), 92.58 (Cϵ), 93.57 (C), 123.05 (C),
(d, J = 8.4 Hz, 2 H, Ar), 7.32 (d, J = 8.4 Hz, 2 H, Ar) ppm. 13C
NMR (100 MHz, CDCl3): δ = 19.25 (SCH3), 82.18 (Cϵ), 90.70
(Cϵ), 121.83 (C), 128.55 (CH), 132.55 (CH), 133.93 (C) ppm. IR
(neat): ν = 2926, 2167 (CϵC), 1506, 1313, 1243, 976, 815, 530 cm–1.
˜
MS (EI): m/z (%) = 182 (100) [M]+, 167 (91), 132 (28). HRMS (EI):
132.76 (CH), 137.40 (CH) ppm. IR (neat): ν = 2954, 2924, 2868,
˜
calcd. for C9H7ClS 181.9952; found 181.9940.
2853, 2165 (CϵC), 1579, 1481, 1454, 1389, 1376, 1255, 1057, 1006,
968, 865, 818, 636, 527 cm–1. MS (EI): m/z (%) = 288 (95) [M]+,
260 (100), 133 (42), 89 (35). HRMS (EI): calcd. for C10H9IS
287.9464; found 287.9466.
2-(2-Naphthyl)ethynyl Methyl Sulfide (1h): Pale yellow oil (71%
yield). 1H NMR (400 MHz, CDCl3): δ = 2.47 (s, 3 H, SCH3), 7.42–
7.45 (m, 3 H, Ar), 7.70–7.75 (m, 3 H, Ar), 7.91 (s, 1 H, Ar) ppm.
13C NMR (100 MHz, CDCl3): δ = 19.39 (SCH3), 81.36 (Cϵ), 92.27
(Cϵ), 120.65 (C), 126.47 (CH), 126.50 (CH), 127.62 (CH), 127.66
(CH), 127.88 (CH), 128.19 (CH), 131.10 (CH), 132.59 (C), 132.90
(4-Bromophenyl)ethynyl Ethyl Sulfide (1q): Pale yellow oil (75%
1
yield). H NMR (400 MHz, CDCl3): δ = 1.43 (t, J = 7.6 Hz, 3 H,
CH3), 2.81 (q, J = 7.6 Hz, 2 H, CH2), 7.25 (d, J = 8.4 Hz, 2 H, Ar),
7.41 (d, J = 8.0 Hz, 2 H, Ar) ppm. 13C NMR (100 MHz, CDCl3): δ
= 14.72 (CH3), 29.91 (CH2), 80.80 (Cϵ), 92.41 (Cϵ), 122.03 (C),
(C) ppm. IR (neat): ν = 2926, 2855, 2156 (CϵC), 1596, 1570, 1500,
˜
1380, 1312, 1270, 1256, 976, 962, 892, 857, 816, 746, 699, 643, 629,
574 cm–1. MS (EI): m/z (%) = 198 (96) [M]+, 183 (100), 139 (83).
HRMS (EI): calcd. for C13H10S 198.0498; found 198.0495.
122.46 (C), 131.48 (CH), 132.70 (CH) ppm. IR (neat): ν = 2959,
˜
2926, 2867, 2855, 2165 (CϵC), 1583, 1484, 1393, 1376, 1255, 1070,
1010, 968, 866, 822, 769, 636, 527 cm–1. MS (EI): m/z (%) = 240
(49) [M]+, 212 (100), 133 (62), 132 (68), 89 (38). HRMS (EI): calcd.
for C10H9BrS 239.9603; found 239.9598.
2-(6-Methoxy-2-naphthyl)ethynyl Methyl Sulfide (1i): Pale yellow
solid (77% yield); m.p. 74–76 °C. H NMR (400 MHz, CDCl3): δ
1
= 2.50 (s, 3 H, SCH3), 3.91 (s, 3 H, OCH3), 7.07 (d, J = 2.4 Hz, 1
H, Ar), 7.13 (dd, J = 8.8 Hz, J = 2.8 Hz, 1 H, Ar), 7.42 (dd, J =
8.4 Hz, J = 2.4 Hz, 1 H, Ar), 7.64 (d, J = 9.2 Hz, 1 H, Ar), 7.66
(d, J = 9.2 Hz, 1 H, Ar), 7.86 (s, 1 H, Ar) ppm. 13C NMR
(100 MHz, CDCl3): δ = 19.49 (SCH3), 55.31 (OCH3), 80.27 (Cϵ),
92.32 (Cϵ), 105.77 (CH), 118.25 (C), 119.36 (CH), 126.73 (CH),
128.40 (C), 128.98 (CH), 129.25 (CH), 131.24 (CH), 134.00 (C),
(4-Chlorophenyl)ethynyl Ethyl Sulfide (1r): Pale yellow oil (81%
1
yield). H NMR (400 MHz, CDCl3): δ = 1.44 (t, J = 7.6 Hz, 3 H,
CH3), 2.81 (q, J = 7.6 Hz, 2 H, CH2), 7.26 (d, J = 8.8 Hz, 2 H, Ar),
7.33 (d, J = 8.8 Hz, 2 H, Ar) ppm. 13C NMR (100 MHz, CDCl3): δ
= 14.72 (CH3), 29.92 (CH2), 80.53 (Cϵ), 92.33 (Cϵ), 122.00 (C),
128.56 (CH), 132.53 (CH), 133.87 (C) ppm. IR (neat): ν = 2963,
˜
158.26 (C) ppm. IR (KBr): ν = 2927, 2853, 2160 (CϵC), 1628,
˜
2926, 2854, 2166 (CϵC), 1486, 1090, 826 cm–1. MS (EI): m/z (%)
= 196 (54) [M]+, 168 (100), 69 (80), 57 (98). HRMS (EI): calcd. for
C10H9ClS 196.0108; found 196.0114.
1600, 1389, 1268, 1237, 1162, 1031, 856, 739 cm–1. MS (EI): m/z
(%) = 228 (100) [M]+, 213 (96). HRMS (EI): calcd. for C14H12OS
228.0603; found 228.0603.
(4-Methoxyphenyl)ethynyl Ethyl Sulfide (1m): Yellow oil (75%
yield). H NMR (400 MHz, CDCl3): δ = 1.43 (t, J = 7.2 Hz, 3 H,
2-(2-Naphthyl)ethynyl Ethyl Sulfide (1s): Pale yellow oil (74%
yield). H NMR (400 MHz, CDCl3): δ = 1.47 (t, J = 7.2 Hz, 3 H,
1
1
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© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2013, 1551–1557

One-Pot Preparation of Ethynyl Sulfides
CH3), 2.83 (q, J = 7.2 Hz, 2 H, CH2), 7.43–7.45 (m, 3 H, Ar), 7.71–
= 8.4 Hz, 2 H, Ar), 7.24 (t, J = 7.6 Hz, 1 H, Ar), 7.36 (t, J =
8.0 Hz, 2 H, Ar), 7.47 (d, J = 7.6 Hz, 2 H, Ar), 7.68 (d, J = 8.4 Hz,
7.77 (m, 3 H, Ar), 7.91 (s, 1 H, Ar) ppm. 13C NMR (100 MHz,
CDCl3): δ = 14.73 (CH3), 29.99 (CH2), 79.66 (Cϵ), 93.90 (Cϵ), 2 H, Ar) ppm. 13C NMR (100 MHz, CDCl3): δ = 77.41 (Cϵ), 94.51
120.80 (C), 126.46 (CH), 127.59 (CH), 127.66 (CH), 127.86 (CH),
128.21 (CH), 130.99 (CH), 132.55 (C), 132.92 (C) ppm. IR (neat):
(Cϵ), 96.81 (C), 122.40 (C), 126.37 (CH), 126.72 (CH), 129.33
(CH), 132.49 (C), 133.04 (CH), 137.57 (CH) ppm. IR (KBr): ν =
˜
ν = 2963, 2926, 2868, 2856, 2155 (CϵC), 1596, 1499, 1453, 1375, 2924, 2853, 2171 (CϵC), 1580, 1478, 1439, 1388, 1005, 900, 816,
˜
1258, 1056, 1018, 963, 891, 857, 816, 746, 699, 641, 628 cm–1. MS
(EI): m/z (%) = 212 (76) [M]+, 184 (100), 139 (43). HRMS (EI):
calcd. for C14H12S 212.0654; found 212.0653.
733, 687, 514 cm–1. MS (EI): m/z (%) = 336 (100) [M]+, 208 (52),
165 (79), 51 (66). HRMS (EI): calcd. for C14H9IS 335.9464; found
335.9462.
2-(6-Methoxy-2-naphthyl)ethynyl Ethyl Sulfide (1t): Pale yellow so-
lid (82% yield); m.p. 49–50 °C. H NMR (400 MHz, CDCl3): δ =
(4-Chlorophenyl)ethynyl Phenyl Sulfide (1y): Pale yellow solid (75%
1
1
yield); m.p. 42–43 °C. H NMR (400 MHz, CDCl3): δ = 7.21–7.49
(m, 9 H, Ar) ppm. 13C NMR (100 MHz, CDCl3): δ = 77.33 (Cϵ),
96.62 (Cϵ), 121.32 (C), 126.28 (CH), 126.68 (CH), 128.75 (CH),
129.32 (CH), 132.52 (C), 132.89 (CH), 134.65 (C) ppm. IR (KBr):
1.47 (t, J = 7.6 Hz, 3 H, CH3), 2.83 (q, J = 7.6 Hz, 2 H, CH2), 3.89
(s, 3 H, OCH3), 7.07 (d, J = 2.0 Hz, 1 H, Ar), 7.13 (dd, J = 8.8 Hz,
J = 2.4 Hz, 1 H, Ar), 7.43 (dd, J = 8.4 Hz, J = 1.2 Hz, 1 H, Ar),
7.63 (d, J = 9.2 Hz, 1 H, Ar), 7.65 (d, J = 9.6 Hz, 1 H, Ar), 7.85
(s, 1 H, Ar) ppm. 13C NMR (100 MHz, CDCl3): δ = 14.73 (CH3),
30.03 (CH2), 55.27 (OCH3), 78.58 (Cϵ), 93.94 (Cϵ), 105.79 (CH),
118.42 (C), 119.33 (CH), 126.70 (CH), 128.41 (C), 128.98 (CH),
129.20 (CH), 131.11 (CH), 133.95 (C), 158.22 (C) ppm. IR (KBr):
ν = 3061, 2169 (CϵC), 1582, 1488, 1478, 1442, 1397, 1092, 1023,
˜
1014, 826, 737, 687, 534 cm–1. MS (EI): m/z (%) = 244 (100) [M]+,
208 (51), 165 (92). HRMS (EI): calcd. for C14H9ClS 244.0108;
found 244.0101.
Typical One-Pot Procedure for the Preparation of Bis(arylethynyl)
Sulfides 2a–2h: LHMDS (1.0 m in THF/ethylbenzene, 2.0 mL) was
added to a solution of bis(arylethanonyl) sulfide (1.0 mmol) in
THF (15 mL) at –78 °C, and the mixture was stirred for 30 min.
Then, ClP(O)(OEt)2 (0.32 mL, 2.2 mmol) was added dropwise at
–78 °C, and the resulting mixture was warmed to room temperature
and stirred for 30 min. The reaction mixture was cooled to –78 °C,
and then LHMDS (1.0 m in THF/ethylbenzene, 5.0 mL) was added.
After stirring at this temperature for 1 h, the reaction was quenched
with an aqueous NH4Cl solution. The mixture was extracted with
AcOEt (3ϫ30 mL). The organic layer was washed with brine, dried
with MgSO4, and filtered. The solvent was evaporated in vacuo,
and the residue was subjected to flash column chromatography (pe-
troleum ether) to give bis(arylethynyl) sulfide 2.
ν = 2963, 2928, 2868, 2839, 2158 (CϵC), 1600, 1498, 1481, 1461,
˜
1389, 1269, 1237, 1031, 968, 941, 853, 805, 768, 662, 632 cm–1. MS
(EI): m/z (%) = 242 (100) [M+], 214 (77), 213 (73), 199 (25), 170
(31). HRMS (EI): calcd. for C15H14OS 242.0760; found 242.0757.
(3-Nitrophenyl)ethynyl Ethyl Sulfide (1u): Red oil (85% yield). 1H
NMR (400 MHz, CDCl3): δ = 1.48 (t, J = 7.6 Hz, 3 H, CH3), 2.87
(q, J = 7.6 Hz, 2 H, CH2), 7.48 (t, J = 8.0 Hz, 1 H, Ar), 7.68 (d, J
= 8.0 Hz, 1 H, Ar), 8.11 (dd, J = 8.4 Hz, J = 1.6 Hz, 1 H, Ar),
8.22 (d, J = 2.0 Hz, 1 H, Ar) ppm. 13C NMR (100 MHz, CDCl3):
δ = 14.75 (CH3), 29.94 (CH2), 83.37 (Cϵ), 91.27 (Cϵ), 122.32
(CH), 125.28 (C), 125.74 (CH), 129.23 (CH), 136.60 (CH), 148.04
(C) ppm. IR (neat): ν = 2967, 2928, 2871, 2830, 2152 (CϵC), 1611,
˜
1570, 1529, 1474, 1353, 1091, 967, 897, 833, 804, 735, 700,
672 cm–1. MS (EI): m/z (%) = 207 (68) [M]+, 179 (100), 133 (69), 89
(47). HRMS (EI): calcd. for C10H9O2NS 207.0349; found 207.0342.
Bis(phenylethynyl) Sulfide (2a):[6a,16] Yellow oil (65% yield). 1H
NMR (400 MHz, CDCl3): δ = 7.26–7.34 (m, 6 H, Ar), 7.47–7.50
(m, 4 H, Ar) ppm. 13C NMR (100 MHz, CDCl3): δ = 71.99 (Cϵ),
94.62 (Cϵ), 122.21 (C), 128.36 (CH), 129.02 (CH), 131.91
(3,4-Methylenedioxyphenyl)ethynyl Ethyl Sulfide (1v): Pale yellow
oil (78% yield). 1H NMR (400 MHz, CDCl3): δ = 1.43 (t, J =
7.6 Hz, 3 H, CH3), 2.79 (q, J = 7.2 Hz, 2 H, CH2), 5.95 (s, 2 H,
CH2), 6.73 (d, J = 8.0 Hz, 1 H, Ar), 6.87 (d, J = 1.2 Hz, 1 H, Ar),
6.95 (dd, J = 8.0 Hz, J = 1.6 Hz, 1 H, Ar) ppm. 13C NMR
(100 MHz, CDCl3): δ = 14.65 (CH3), 29.92 (CH2), 77.16 (Cϵ),
93.13 (Cϵ), 101.22 (CH2), 108.30 (CH), 111.64 (CH), 116.71 (C),
(CH) ppm. IR (neat): ν = 2924, 2853, 2175 (CϵC), 1595, 1573,
˜
1487, 1442, 1376, 1176, 1069, 1026, 915, 861, 754, 688, 536 cm–1.
MS (EI): m/z (%) = 234 (100) [M]+, 189 (78), 95 (54). HRMS (EI):
calcd. for C16H10S 234.0498; found 234.0493.
126.39 (CH), 147.27 (C), 147.75 (C) ppm. IR (neat): ν = 2966, 2926,
˜
Bis(4-methoxyphenylethynyl) Sulfide (2b): Colorless crystals (64%
yield); m.p. 87–88 °C. H NMR (400 MHz, CDCl3): δ = 3.73 (s, 6
H, OCH3), 6.76 (d, J = 8.8 Hz, 4 H, Ar), 7.35 (d, J = 8.8 Hz, 4 H,
Ar) ppm. 13C NMR (100 MHz, CDCl3): δ = 55.27 (OCH3), 70.61
(Cϵ), 94.40 (Cϵ), 113.97 (CH), 114.33 (C), 133.87 (CH), 160.25
1
2895, 2830, 2162 (CϵC), 1602, 1503, 1487, 1439, 1332, 1246, 1203,
1129, 1098, 1039, 968, 933, 860, 810, 770, 719, 661, 636, 613,
576 cm–1. MS (EI): m/z (%) = 206 (89) [M]+, 178 (98), 177 (100),
147 (28). HRMS (EI): calcd. for C11H10O2S 206.0396; found
206.0387.
(C) ppm. IR (KBr): ν = 2973, 2948, 2838, 2167 (CϵC), 1602, 1568,
˜
1507, 1436, 1295, 1248, 1190, 1172, 1031, 935, 828, 773, 642,
536 cm–1. MS (EI): m/z (%) = 294 (100) [M]+, 279 (32), 235 (43),
125 (30). HRMS (EI): calcd. for C18H14O2S 294.0709; found
294.0704.
(2,5-Dimethoxyphenyl)ethynyl Phenyl Sulfide (1w): Yellow oil (74%
yield). 1H NMR (400 MHz, CDCl3): δ = 3.77 (s, 3 H, OCH3), 3.87
(s, 3 H, OCH3), 6.82 (d, J = 8.8 Hz, 1 H, Ar), 6.87 (dd, J = 9.2 Hz,
J = 2.8 Hz, 1 H, Ar), 7.00 (d, J = 2.4 Hz, 1 H, Ar), 7.22 (t, J =
7.6 Hz, 1 H, Ar), 7.35 (t, J = 8.0 Hz, 2 H, Ar), 7.54 (dd, J = 8.0 Hz,
J = 1.2 Hz, 2 H, Ar) ppm. 13C NMR (100 MHz, CDCl3): δ = 55.78
(OCH3), 56.36 (OCH3), 79.15 (Cϵ), 94.55 (Cϵ), 111.89 (CH),
112.58 (C), 115.87 (CH), 117.73 (CH), 125.95 (CH), 126.31 (CH),
Bis[(2,5-dimethoxyphenyl)ethynyl] Sulfide (2c): White solid (63%
1
yield); m.p. 106–107 °C. H NMR (400 MHz, CDCl3): δ = 3.75 (s,
6 H, OCH3), 3.84 (s, 6 H, OCH3), 6.79 (d, J = 8.8 Hz, 2 H, Ar),
6.87 (dd, J = 9.0 Hz, J = 3.0 Hz, 2 H, Ar), 6.98 (d, J = 3.2 Hz, 2 H,
Ar) ppm. 13C NMR (100 MHz, CDCl3): δ = 55.78 (OCH3), 56.39
(OCH3), 75.80 (Cϵ), 90.88 (Cϵ), 111.91 (C), 112.09 (CH), 116.76
129.15 (CH), 133.10 (C), 153.09 (C), 154.67 (C) ppm. IR (neat): ν
˜
= 3058, 2999, 2833, 2165 (CϵC), 1867, 1604, 1578, 1498, 1441,
1307, 1230, 1165, 1045, 1023, 903, 805, 738, 688, 604 cm–1. MS
(EI): m/z (%) = 270 (100) [M]+, 255 (25), 227 (30), 184 (25). HRMS
(EI): calcd. for C16H14O2S 270.0709; found 270.0707.
(CH), 118.29 (CH), 153.08 (C), 155.07 (C) ppm. IR (KBr): ν =
˜
2939, 2833, 2167 (CϵC), 1604, 1576, 1498, 1462, 1441, 1305, 1271,
1230, 1164, 1136, 1042, 805, 729, 656, 602 cm–1. MS (EI): m/z (%)
= 354 (100) [M]+, 324 (73), 162 (54), 147 (40). HRMS (EI): calcd.
(4-Iodophenyl)ethynyl Phenyl Sulfide (1x): Pale yellow solid (86%
1
yield); m.p. 58–60 °C. H NMR (400 MHz, CDCl3): δ = 7.22 (d, J for C20H18O4S 354.0920; found 354.0913.
Eur. J. Org. Chem. 2013, 1551–1557
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
1555

Q.-Y. Cai, Z.-H. Peng, D.-L. An et al.
FULL PAPER
Bis(4-methylphenylethynyl) Sulfide (2d): Colorless crystal oil (76%
yield); m.p. 53–55 °C. H NMR (400 MHz, CDCl3): δ = 2.33 (s, 6
bridge Crystallographic Data Center via www.ccdc.cam.ac.uk/
data_request/cif.
1
H, CH3), 7.11 (d, J = 8.0 Hz, 4 H, Ar), 7.36 (d, J = 8.0 Hz, 4 H,
Ar) ppm. 13C NMR (100 MHz, CDCl3): δ = 21.52 (CH3), 71.26
(Cϵ), 94.67 (Cϵ), 119.17 (C), 129.08 (CH), 131.92 (CH), 139.31
Studies of the Reaction Mechanism
(i) Trapping of Diethyl 2-(Methylthio)-1-phenylvinyl Phosphate (3a):
LHMDS (1.0 m in THF/ethylbenzene, 1.5 mL) was added to a solu-
tion of phenylethanonyl methyl sulfide (249 mg, 1.5 mmol) in THF
(15 mL) at –78 °C, and the mixture was stirred for 30 min. Then,
ClP(O)(OEt)2 (0.26 mL, 1.8 mmol) was added dropwise at –78 °C,
and the resulting mixture was warmed to room temperature and
stirred for 30 min. The reaction was quenched with an aqueous
NH4Cl solution. The mixture was extracted with AcOEt
(3ϫ30 mL). The organic layer was washed with brine, dried with
MgSO4, and filtered. The solvent was evaporated in vacuo, and the
residue was subjected to flash column chromatography (petroleum
ether/CH2Cl2, 2:1) to give intermediate 3a (Z/E, 93:7; 362 mg,
1.2 mmol, 80%) as a yellow oil. Data for (Z)-3a: 1H NMR
(400 MHz, CDCl3): δ = 1.27 (t, J = 7.2 Hz, 6 H, CH3), 2.39 (s, 3
H, SCH3), 4.08–4.24 (m, 4 H, CH2), 6.09 (d, JP,H = 2.0 Hz, 1 H,
=CH), 7.27 (t, J = 7.2 Hz, 1 H, Ar), 7.33 (t, J = 7.2 Hz, 2 H, Ar),
7.48 (d, J = 7.2 Hz, 2 H, Ar) ppm. 13C NMR (100 MHz, CDCl3):
(C) ppm. IR (KBr): ν = 2920, 2859, 2171 (CϵC), 1605, 1506, 1455,
˜
1378, 1246, 1179, 1020, 814, 532 cm–1. MS (EI): m/z (%) = 262
(100) [M]+, 218 (27), 202 (24). HRMS (EI): calcd. for C18H14S
262.0811; found 262.0804.
Bis(4-iodophenylethynyl) Sulfide (2e): Pale yellow solid (74% yield);
m.p. 155–156 °C. 1H NMR (400 MHz, CDCl3): δ = 7.19 (d, J =
8.4 Hz, 4 H, Ar), 7.67 (d, J = 8.4 Hz, 4 H, Ar) ppm. 13C NMR
(100 MHz, CDCl3): δ = 73.24 (Cϵ), 93.95 (Cϵ), 95.26 (C), 121.57
(C), 133.23 (CH), 137.60 (CH) ppm. IR (KBr): ν = 2924, 2854,
˜
2166 (CϵC), 1577, 1463, 1388, 1232, 1090, 1054, 1006, 815, 745,
698, 675, 533 cm–1. MS (EI): m/z (%) = 486 (21) [M]+, 441 (15), 188
(27), 187 (26). HRMS (EI): calcd. for C16H8I2S 485.8431; found
485.8431.
Bis(4-chlorophenylethynyl) Sulfide (2f): Colorless crystals (70%
yield); m.p. 108–110 °C. 1H NMR (400 MHz, CDCl3): δ = 7.30 (d,
J = 8.8 Hz, 4 H, Ar), 7.41 (d, J = 8.8 Hz, 4 H, Ar) ppm. 13C NMR
(100 MHz, CDCl3): δ = 72.83 (Cϵ), 93.66 (Cϵ), 120.55 (C), 128.76
δ = 15.98 (d, JP,C = 7.1 Hz, CH3), 17.25 (SCH3), 64.55 (d, JP,C
=
5.8 Hz, CH2), 115.82 (d, JP,C = 7.4 Hz, =CH), 124.89 (CH), 128.09
(CH), 128.24 (CH), 134.59 (C), 143.67 (d, JP,C = 9.0 Hz, =C-
O) ppm. 31P NMR (162 MHz, CDCl3): δ = –5.43 (s) ppm. IR
(CH), 133.10 (CH), 135.25 (C) ppm. IR (KBr): ν = 2956, 2926,
˜
2163 (CϵC), 1587, 1486, 1398, 1253, 1172, 1088, 1057, 1015, 926,
897, 824, 702, 541 cm–1. MS (EI): m/z (%) = 302 (100) [M]+, 258
(30), 223 (43), 187 (17). HRMS (EI): calcd. for C16H8Cl2S
301.9718; found 301.9727.
(KBr): ν = 2984, 2926, 2360, 2342, 1608 (C=C), 1573, 1492, 1444,
˜
1394, 1369, 1271 (P=O), 1165, 1023, 983, 906, 761, 736, 695, 632,
507 cm–1. MS (EI): m/z (%) = 302 (27) [M]+, 148 (100). HRMS
(EI): calcd. for C13H19O4PS 302.0736; found 302.0730. Data for
Bis[2-(2-naphthyl)ethynyl] Sulfide (2g): White solid (72% yield);
1
1
m.p. 102–105 °C. H NMR (400 MHz, CDCl3): δ = 7.49–7.56 (m,
(E)-3a: H NMR (400 MHz, CDCl3): δ = 1.34 (t, J = 7.2 Hz, 6 H,
6 H, Ar), 7.78–7.83 (m, 6 H, Ar), 8.04 (s, 2 H, Ar) ppm. 13C NMR
CH3), 2.33 (s, 3 H, SCH3), 4.08–4.24 (m, 4 H, CH2), 6.31 (d, JP,H
(100 MHz, CDCl3): δ = 72.28 (Cϵ), 95.18 (Cϵ), 119.50 (C), 126.69 = 2.4 Hz, 1 H, =CH), 7.27 (t, J = 7.2 Hz, 1 H, Ar), 7.39 (t, J =
(CH), 127.08 (CH), 127.79 (CH), 127.89 (CH), 128.09 (CH), 128.19
7.2 Hz, 2 H, Ar), 7.60 (d, J = 7.6 Hz, 2 H, Ar) ppm. 31P NMR
(CH), 132.20 (CH), 132.83 (C), 133.12 (C) ppm. IR (KBr): ν = (162 MHz, CDCl3): δ = –5.33 (s) ppm.
˜
2926, 2856, 2159 (CϵC), 1591, 1569, 1498, 1458, 1382, 1364, 1273,
(ii) Elimination of Enol Phosphate 3a: LHMDS (1.0 m in THF/eth-
1258, 1214, 963, 899, 862, 821, 747, 699 cm–1. MS (EI): m/z (%) =
334 (100) [M]+, 289 (37). HRMS (EI): calcd. for C24H14S 334.0811;
found 334.0806.
ylbenzene, 2.5 mL) was added to a solution of intermediate 3a
(302 mg, 1.0 mmol) in THF (15 mL) at –78 °C. When 3a was con-
sumed (monitored by TLC), the reaction was quenched with an
aqueous NH4Cl solution, and the resulting mixture was extracted
with AcOEt (3ϫ30 mL). The organic layer was washed with brine,
dried with MgSO4, and filtered. The solvent was evaporated in
vacuo, and the residue was subjected to flash column chromatog-
raphy (petroleum ether) to give phenylethynyl methyl sulfide 1a
(135 mg, 0.9 mmol, 91%) as a colorless oil.
Bis[2-(6-methoxy-2-naphthyl)ethynyl] Sulfide (2h): Colorless crystals
(71% yield); m.p. 127–129 °C. 1H NMR (400 MHz, CDCl3): δ =
3.92 (s, 6 H, OCH3), 7.10 (d, J = 2.4 Hz, 2 H, Ar), 7.16 (dd, J =
8.8 Hz, J = 2.4 Hz, 2 H, Ar), 7.49 (d, J = 8.8 Hz, 2 H, Ar), 7.67
(d, J = 9.6 Hz, 2 H, Ar), 7.70 (d, J = 9.2 Hz, 2 H, Ar), 7.96 (s, 2
H, Ar) ppm. 13C NMR (100 MHz, CDCl3): δ = 55.37 (OCH3),
71.58 (Cϵ), 95.23 (Cϵ), 105.88 (CH), 117.14 (C), 119.56 (CH),
126.87 (CH), 128.32 (C), 128.98 (CH), 129.47 (CH), 132.20 (CH),
Supporting Information (see footnote on the first page of this arti-
cle): Synthetic details and characterization data for 2-bromo-1-
arylethanone and substrates [arylethanonyl sulfides and bis(aryl-
ethanonyl) sulfides]. Characterization data for arylethynyl sulfides
(1a–1f and 1j–1l), crystal structure determination and refinement,
1H and 13C NMR spectra of substrates and products [arylethynyl
134.56 (C), 158.67 (C) ppm. IR (KBr): ν = 2932, 2845, 2165
˜
(CϵC), 1597, 1558, 1539, 1456, 1387, 1331, 1267, 1232, 1118, 1068,
1028, 964, 940, 895, 857, 814, 711, 666, 639 cm–1. MS (EI): m/z (%)
= 394 (100) [M]+, 379 (25), 214 (35), 182 (58), 139 (43). HRMS
(EI): calcd. for C26H18O2S 394.1022; found 394.1036. The crystal
for X-ray diffraction was grown in a solution of dichloromethane
and petroleum ether. X-ray crystal structure data for 2h:
C26H18O2S, M = 394.46, monoclinic, a = 11.1239(13) Å, b =
10.3796(12) Å, c = 17.756(2) Å, α = 90°, β = 100.371(2)°, γ = 90°,
V = 2016.6(4) Å3, space group P21/c, Z = 4, calculated density
1.299 Mgm–3, crystal dimensions (mm3): 0.39ϫ0.32ϫ0.15, T =
293(2) K, λ(Mo-Kα) = 0.71073 Å, μ = 0.180 mm–1, 11605 reflec-
tions collected, 4394 independent (Rint = 0.0463), 264 parameter
refined on F2, R1 = 0.0873, wR2[F2] = 0.1245 (all data), goodness-
of-fit (GOF) on F2 = 0.936, Δρmax = 0.223 eÅ–3. CCDC-888793
(for 2h) contains the supplementary crystallographic data for this
paper. These data can be obtained free of charge from The Cam-
1
sulfides and bis(arylethynyl) sulfides], and H, 13C, and 31P NMR
spectra and NOESY spectra of intermediate 3a.
Acknowledgments
The authors are grateful for financial support from the National
Natural Science Foundation of China (NSFC) (grant number
21072052), the National Basic Research Program of China (grant
number 2009CB421601), and the Hunan Provincial Science and
Technology Department Program (grants 2011WK4007 and
06FJ4115).
1556
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© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2013, 1551–1557

One-Pot Preparation of Ethynyl Sulfides
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Received: October 24, 2012
Published Online: January 29, 2013
Eur. J. Org. Chem. 2013, 1551–1557
© 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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