A novel stereoselective synthesis of (z)-α-arylsulfanyl-α, β-unsaturated ketones via stille coupling of (E)-α- Arylsulfanylvinylstannanes with acyl halides

Article abstract of DOI:10.1002/hc.20536

(E)-α-Arylsulfanylvinylstannanes react with acyl halides in the presence of a catalytic amount of Pd(PPh₃)₄ and CuI cocatalyst to give stereoselectively the corresponding (Z)-α-arylsulfanyl- α,β-unsaturated ketones in good yields.

Full text of DOI:10.1002/hc.20536

Heteroatom Chemistry
Volume 20, Number 4, 2009
A Novel Stereoselective Synthesis of
(Z)-α-Arylsulfanyl-α,β-Unsaturated Ketones
via Stille Coupling of (E)-α-
Arylsulfanylvinylstannanes with Acyl Halides
Fang Yao,1,2 Shengyong You,1 and Mingzhong Cai1
1School of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang 330022,
People’s Republic of China
2Department of Chemistry and Pharmaceutical Engineering, West Branch of Zhejiang University
of Technology, Quzhou 324000, People’s Republic of China
Received 10 February 2009; revised 11 April 2009
with olefins is also an important route to the α,β-
ABSTRACT: (E)-α-Arylsulfanylvinylstannanes re-
unsaturated ketones [3]. The hydrozirconation of
act with acyl halides in the presence of a cat-
alkynes, followed by aluminum chloride promoted
alytic amount of Pd(PPh3)4 and CuI cocatalyst
acylation of the resulting vinylzirconium com-
to give stereoselectively the corresponding (Z)-α-
pounds, has provided a convenient method for stere-
arylsulfanyl-α,β-unsaturated ketones in good yields.
oselective synthesis of α,β-unsaturated ketones [4].
ꢀ
C
2009 Wiley Periodicals, Inc. Heteroatom Chem 20:218–
The synthesis of heteroatom-containing α,β-
unsaturated ketones has also attracted consider-
able interest in organic synthesis because many
223, 2009; Published online in Wiley InterScience
(www.interscience.wiley.com). DOI 10.1002/hc.20536
useful functional group transformations can be
achieved by introduction and removal of het-
INTRODUCTION
eroatom functions. Sung et al. reported that hy-
drozirconation of acetylenic tellurides, followed by
the reaction with acyl halides in the presence
of CuI, gave α-organotelluro-α,β-unsaturated ke-
tones [5]. Zhao and Huang described the synthe-
sis of (Z)-β-selenyl-α,β-unsaturated ketones by CuX-
catalyzed selenocarbonylation addition reaction of
selenoesters to nonactivated terminal alkynes [6].
(Z)-α-Selenyl-α,β-unsaturated ketones could be pre-
pared by utilizing either a Wittig-type reaction of
α-phenylselanyl arsonium ylides with carbonyl com-
pounds [7] or through palladium-catalyzed acyla-
tion of (E)-α-selanylvinylstannanes with acyl halides
[8]. α-Arylthio- or alkylthio-α,β-unsaturated ke-
tones are very useful synthetic intermediates [9–12].
For example, they have been used in preparation
of 2,3-dihydrofurans [13], 1,4- and 1,5-dicarbonyl
α,β-Unsaturated ketones are one of the most widely
used synthetic building blocks, and a variety of syn-
thetic methods for the synthesis of α,β-unsaturated
ketones have been reported. Of these methods,
the aldol condensation is one of the most pow-
erful synthetic tools for them [1,2]. The Friedel–
Crafts reaction of acyl chlorides, acids, or anhydrides
Correspondence to: Mingzhong Cai; e-mail: caimzhong@
163.com.
Contract grant sponsor: National Natural Science Foundation
of China.
Contract grant number: 20862008.
Contract grant sponsor: Natural Science Foundation of Jiangxi
Province in China.
Contract grant number: 2007GZW0172.
2009 Wiley Periodicals, Inc.
c
ꢀ
218

A Novel Stereoselective Synthesis of (Z)-α-Arylsulfanyl-α,β-Unsaturated Ketones 219
compounds [14], in the regioselective alkylation of
as vinyl sulfides. Vinylstannanes can undergo the
Stille coupling with organic halides [27,28]. The cou-
pling reaction of (E)-α-arylsulfanylvinylstannanes
with vinylic halides was conducted in the pres-
ence of a palladium-copper cocatalyst and gave 2-
arylsulfanyl-substituted 1,3-dienes stereoselectively
[29]. With the extended application of the (E)-α-
arylsulfanylvinylstannanes in organic synthesis, we
attempted to carry out the coupling reaction of (E)-
α-arylsulfanylvinylstannanes with acyl halides in the
presence of a palladium-copper cocatalyst.
cyclohexanones [11]. Some methods for the synthe-
sis of α-arylthio- or alkylthio-α,β-unsaturated ke-
tones have been developed including the Pummerer
rearrangement of 2-arylsulfinyl ketones [15–17], the
NaOH-catalyzed thiolysis of α,β-epoxyketones [18],
and the Rh-catalyzed diazo decomposition of the
β-thio group α-diazo ketones [19]. Despite consid-
erable methodological differentiation, the reported
procedures usually require starting materials which
are not readily available, there still exists a need
for new selective and convenient methods. Our
group has reported the Stille coupling reactions
of (E)-α-arylsulfanyl- or selenenyl-substituted vinyl-
stannanes with organic halides in the presence of
a catalytic amount of Pd(PPh3)4 and CuI cocata-
lyst, providing new methods for stereoselective syn-
thesis of 1,2-disubstituted vinyl sulfides [20] and
2-selenenyl-substituted 1,3- and 1,4-dienes [21,22].
Very recently, we have found that (E)-α-arylsulfonyl-
substituted vinylstannanes can also be coupled with
aryl iodides or alkynyl bromides in the presence
of Pd(PPh3)4 and CuI cocatalyst, to afford 1,2-
disubstituted vinyl sulfones [23] and 2-sulfonyl-
substituted 1,3-enynes [24], respectively. However,
to the best of our knowledge, there has been no
general study of the Stille coupling reaction of (E)-
α-arylsulfanylvinylstannanes with acyl halides de-
scribed to date. Herein we wish to report that (Z)-α-
arylsulfanyl-α,β-unsaturated ketones can be conve-
niently synthesized by the Stille coupling reaction of
(E)-α-arylsulfanylvinylstannanes with acyl halides
in the presence of a catalytic amount of Pd(PPh3)4
and CuI cocatalyst in good yields.
Initially, to determine the optimum conditions,
the cross-coupling reaction of benzoyl chloride
(1.1 equiv) with (E)-1-(4-methylphenyl)sulfanyl-1-
tributylstannyl-1-hexene was examined under var-
ious reaction conditions (Scheme 1). The results
are summarized in Table 1. Among the palladium-
phosphine complexes screened, Pd(PPh3)4 showed
the best catalytic activity (yield 82%); whereas the
yields were low in the presence of other palladium-
phosphine complexes such as PdCl2(PPh3)2 (21%),
PdBnCl(PPh3)2 (29%), and PdCl2(dppe) (trace) even
under sealed-tube conditions. Phosphine-free pal-
ladium catalysts such as PdCl2, Pd(OAc)2, and
Pd2(dba)3 exhibited no catalytic activity for the reac-
tion. It was found that benzene was the best solvent
among those tested, such as DMF, THF, CH2Cl2, and
toluene. The same reaction performed in toluene af-
forded the coupled product in moderate yield. The
cross-coupling reaction proceeded smoothly in ben-
zene at reflux temperature in the presence of 5 mol%
Pd(PPh3)4 and 75 mol% CuI, affording the corre-
sponding coupled product in 82% yield after 7 h;
while the same reaction under sealed-tube condi-
tions gave the coupled product in only 83% yield. The
reaction did not occur in the presence of Pd(PPh3)4
without the cocatalyst (CuI) after 72 h even under
sealed-tube conditions. It may be a possible mecha-
nistic explanation for the role of CuI that a prelimi-
nary transmetallation from the organostannane to a
more reactive organocopper intermediate has taken
place during the Stille coupling reaction [30]. Tin to
copper transmetallation has also been suggested in
other studies, utilizing organostannanes in conjunc-
tion with copper [31–34]. On the other hand, the
reaction also did not occur in the presence of CuI
without any palladium catalyst.
RESULTS AND DISCUSSION
Palladium-catalyzed hydrostannylation of alkynes
provides a simple, general route for the synthesis of
vinylstannanes [25]. Palladium-catalyzed hydrostan-
nylation of arylsulfanylalkynes has been reported
to be high regio- and stereoselective, giving (E)-α-
arylsulfanylvinylstannanes in high yields [26]. (E)-
α-Arylsulfanylvinylstannanes are the difunctional
group reagents in which two synthetically versatile
groups are linked to the same olefinic carbon atom
and can be considered both as vinylstannanes and
C4H9
H
SC6H4CH3-4
Ph
O
C4H9
H
SC6H4CH3-4
SnBu3
Cat.
+
C
C
Ph
Cl
O
SCHEME 1
Heteroatom Chemistry DOI 10.1002/hc

220 Yao, You, and Cai
TABLE 1 Cross-Coupling of (E)-1-(4-Methylphenyl)sulfanyl-1-tributylstannyl-1-hexene with Benzoyl Chloridea
Catalystb
Additivec
Solvent
Temp. (◦C)
Time (h)
Yield (%)d
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(PPh3)2
PdCl2(PPh3)2
PdBnCl(PPh3)2
PdBnCl(PPh3)2
PdBnCl(PPh3)2
PdCl2(dppe)
PdCl2(dppe)
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
CuI
DMF
C6H6
C6H6
THF
r.t.e (or 65◦C)
r.t. (or reflux)
120 (sealed tube)
r.t. (or reflux)
120 (sealed tube)
r.t. (or 65 ◦C)
120 (sealed tube)
120 (sealed tube)
r.t. (or 65 ◦C)
Reflux or 120
r.t. (or 65 ◦C)
120 (sealed tube)
120 (sealed tube)
r.t.
Reflux
Reflux
120 (sealed tube)
Reflux
Reflux or 120
Reflux or 120
72
72
72
72
72
72
72
72
72
72
72
72
72
72
4
0
0
21
0
0
0
29
Trace
0
Trace
0
0
0
0
77
82
83
48
0
THF
DMF
C6H6
THF
DMF
C6H6
DMF
THF
CH2Cl2
C6H6
C6H6
C6H6
C6H6
Toluene
C6H6
C6H6
7
7
24
72
72
CuI
0
aReaction was carried out with 1.0 mmol of (E)-1-(4-methylphenyl)sulfanyl-1-tributylstannyl-1-hexene and 1.1 mmol of benzoyl chloride under
argon.
b5 mol% of Pd catalyst was used.
c0.75 (equiv) CuI was used.
dIsolated yield.
er.t. = Room temperature.
SAr
The Stille coupling reactions of a variety of
(E)-α-arylsulfanylvinylstannanes with acyl halides
were examined in the presence of a catalytic
amount (5 mol%) of Pd(PPh3)4 and CuI (0.75
equiv) in benzene at reflux temperature (Scheme 2),
and the results are summarized in Table 2. In
all cases, the reaction proceeded smoothly to af-
ford the corresponding coupled products in good
yields. Electron-donating and electron-withdrawing
groups such as CH3, Cl, and NO2 on aromatic
acyl halides were well tolerated. Unfortunately, the
R
O
C
SAr
R
H
Pd(PPh3)4/CuI
Benzene, reflux
+
R1
C
O
H
SnBu3
R1
Cl
3
1
2
SCHEME 2
Stille coupling of (E)-α-arylsulfanylvinylstannanes
with aliphatic acyl halides did not occur under the
same conditions. To get insight into the stereos-
electivity of this coupling reaction, we prepared
TABLE 2 Synthesis of (Z)-α-Arylsulfanyl-α,β-unsaturated Ketones
Entry
R
Ar
R1
Product
Yield (%)a
1
2
3
4
5
6
7
8
n-C4H9
n-C4H9
n-C4H9
n-C4H9
CH3OCH2
CH3OCH2
CH3OCH2
CH3OCH2
CH3OCH2
Ph
Ph
Ph
Ph
3a
3b
3c
3d
3e
3f
3g
3h
3i
81
80
82
79
76
81
73
75
77
86
79
4-O2NC6H4
Ph
4-ClC6H4
Ph
4-CH3C6H4
4-ClC6H4
4-O2NC6H4
Ph
4-CH3C6H4
4-CH3C6H4
Ph
Ph
Ph
Ph
9
10
11
4-CH3C6H4
Ph
4-ClC6H4
Ph
4-ClC6H4
3j
3k
Ph
aIsolated yield based on the (E)-α-arylsulfanylvinylstannane 1 used.
Heteroatom Chemistry DOI 10.1002/hc

A Novel Stereoselective Synthesis of (Z)-α-Arylsulfanyl-α,β-Unsaturated Ketones 221
(Z)-α-arylsulfanylvinylstannanes by hydrozircona-
(2.0 mL) under argon, Pd(PPh3)4 (0.05 mmol) and
CuI (0.75 mmol) were added, the resulting mixture
was stirred at reflux for 7 h, cooled to room tem-
perature, and diluted with light petroleum. The su-
pernatant was filtered through a short plug of silica
gel and the filtrate evaporated. The residue was pu-
rified by preparative TLC on silica gel to afford the
corresponding compounds.
tion of alkynylstannanes, followed by the reac-
tion with arylsulfenyl chlorides. We investigated
the cross-coupling reaction of (Z)-α-arylsulfanyl-
vinylstannanes with acyl chlorides under the same
conditions, and it was found that the cross-coupling
reaction did not occur even under sealed-tube con-
ditions due to the presence of steric hindrance. It
is well documented that the Stille coupling reac-
tion of vinylstannanes with organic halides, in the
presence of a palladium catalyst, occurs with re-
tention of configuration [27, 35]. In addition, the
Z-configuration of compound 3c was confirmed by
NOESY experiments. An enhancement of the allylic
protons was observed as the vinylic proton of 3c
was irradiated. A correlation between the allylic pro-
tons and the aromatic protons (δ = 7.14) of the
(4-methylphenyl)sulfanyl group was observed. The
NOE results indicate that compound 3c has the ex-
pected Z-configuration and that the cross-coupling
reaction of (E)-α-arylsulfanylvinylstannanes with
acyl halides occurs with retention of configuration.
In conclusion, a new method for the stereoselec-
tive synthesis of (Z)-α-arylsulfanyl-α,β-unsaturated
ketones has been developed based on the Stille cou-
pling reaction of (E)-α-arylsulfanylvinylstannanes
with acyl halides. This shows the usefulness of
(E)-α-arylsulfanylvinylstannanes for the synthesis
of highly functionalized organosulfur compounds.
The investigations of the synthetic applications of
(Z)-α-arylsulfanyl-α,β-unsaturated ketones are in
progress.
(Z)-1-Benzoyl-1-phenylthio-1-hexene 3a. Oil. IR
(film): ν (cm−1) 3060, 2928, 1665, 1597, 1447, 1258,
1
741, 690; H NMR (400 MHz, CDCl3): δ 7.69 (d, J
= 8.4 Hz, 2H), 7.49–7.47 (m, 1H), 7.37 (t, J = 7.6
Hz, 2H), 7.24–7.10 (m, 5H), 6.73 (t, J = 7.2 Hz, 1H),
2.61–2.55 (m, 2H), 1.52–1.48 (m, 2H), 1.43–1.38 (m,
2H), 0.94 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz,
CDCl3): δ 194.11, 149.69, 137.45, 135.72, 134.40,
132.34, 129.88, 129.39, 128.93, 128.12, 126.63, 30.69,
30.33, 22.54, 13.89; MS (EI, 70 eV): m/z 296 (M+,
100), 105 (93), 77 (45); Anal. calcd for C19H20OS: C,
77.00; H, 6.80. Found: C, 76.74; H, 6.61.
(Z)-1-(4-Nitrobenzoyl)-1-phenylthio-1-hexene 3b.
Oil. IR (film): ν (cm−1) 2928, 1670, 1592, 1519, 1345,
848, 690; 1H NMR (400 MHz, CDCl3): δ 8.07 (d,
J = 8.8 Hz, 2H), 7.68 (d, J = 8.8 Hz, 2H), 7.18–
7.06 (m, 5H), 6.55 (t, J = 7.2 Hz, 1H), 2.63–2.57
(m, 2H), 1.55–1.50 (m, 2H), 1.45–1.37 (m, 2H), 0.95
(t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3):
δ 194.52, 147.01, 143.50, 134.72, 132.38, 129.32,
128.93, 128.58, 128.13, 126.07, 123.53, 31.31, 30.99,
22.50, 13.97; MS (EI, 70 eV): m/z 341 (M+, 9.3), 109
(100), 57 (35); Anal. calcd for C19H19NO3S: C, 66.85;
H, 5.61. Found: C, 66.56; H, 5.69.
EXPERIMENTAL
1H NMR spectra were recorded on a Bruker AC-P400
(400 MHz) spectrometer with TMS as an internal
standard using CDCl3 as the solvent. 13C NMR
(100 MHz) spectra were recorded on a Bruker AC-
P400 (400 MHz) spectrometer using CDCl3 as the
solvent. IR spectra were determined on an FTS-185
instrument as neat films. Mass spectra were obtained
on a Finnigan 8239 mass spectrometer. Microanal-
yses were measured using a Yanaco MT-3 CHN mi-
croelemental analyzer. All reactions were carried out
in predried glassware (150◦C, 4 h) and cooled under
a stream of dry argon. Benzene and THF were dis-
tilled from sodium prior to use. DMF was dried by
distillation over calcium hydride.
(Z)-1-Benzoyl-1-(4-methylphenyl)thio-1-hexene
3c. Oil. IR (film): ν (cm−1) 2927, 1666, 1596, 1448,
1
1258, 1089, 806, 717; H NMR (400 MHz, CDCl3):
δ 7.69 (d, J = 8.4 Hz, 2H), 7.51–7.49 (m, 1H), 7.38
(t, J = 7.6 Hz, 2H), 7.14 (d, J = 8.0 Hz, 2H),
6.98 (d, J = 8.0 Hz, 2H), 6.64 (t, J = 7.6 Hz, 1H),
2.59–2.54 (m, 2H), 2.24 (s, 3H), 1.51–1.44 (m, 2H),
1.42–1.35 (m, 2H), 0.94 (t, J = 7.2 Hz, 3H); 13C NMR
(100 MHz, CDCl3): δ 194.15, 148.43, 137.53, 136.80,
136.36, 132.28, 130.53, 129.70, 129.42, 128.00,
127.48, 30.73, 30.21, 22.53, 21.00, 13.89; MS (EI, 70
eV): m/z 310 (M+, 37), 186 (25), 105 (100), 91 (43);
Anal. calcd for C20H22OS: C, 77.39; H, 7.14. Found:
C, 77.15; H, 6.95.
General Procedure for the Synthesis of
(Z)-α-Arylsulfanyl-α,β-Unsaturated Ketones
(3a–k)
(Z)-1-(4-Chlorobenzoyl)-1-(4-methylphenyl)thio-
1-hexene 3d. Oil. IR (film): ν (cm−1) 2926, 1667,
1588, 1492, 1253, 1091, 806, 756; 1H NMR (400 MHz,
CDCl3): δ 7.63 (d, J = 8.4 Hz, 2H), 7.34 (d, J = 8.4 Hz,
2H), 7.10 (d, J = 8.0 Hz, 2H), 6.98 (d, J = 8.0 Hz,
To a solution of (E)-α-arylsulfanylvinylstannane
(1.0 mmol) and acyl halide (1.1 mmol) in benzene
Heteroatom Chemistry DOI 10.1002/hc

222 Yao, You, and Cai
2H), 6.61 (t, J = 7.2 Hz, 1H), 2.60–2.54 (m, 2H), 2.24
(s, 3H), 1.53–1.49 (m, 2H), 1.44–1.38 (m, 2H), 0.95
(t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3):
δ 193.00, 147.82, 138.66, 137.04, 136.11, 135.74,
135.02, 130.76, 130.67, 129.76, 128.39, 30.74, 30.13,
22.53, 21.02, 13.90; MS (EI, 70 eV): m/z 346 (M+,
37Cl, 16), 344 (M+, 35Cl, 45), 139 (100), 91 (29); Anal.
calcd for C20H21OSCl: C, 69.65; H, 6.14. Found: C,
69.38; H, 5.86.
= 5.6 Hz, 1H), 4.43 (d, J = 5.6 Hz, 2H), 3.46 (s,
3H); 13C NMR (100 MHz, CDCl3): δ 193.41, 145.63,
137.74, 134.97, 133.47, 130.19, 129.37, 129.06,
128.46, 126.70, 123.58, 70.68, 58.68; MS (EI, 70 eV):
m/z 329 (M+, 53), 298 (25), 115 (91), 109 (100); Anal.
calcd for C17H15NO4S: C, 62.00; H, 4.59. Found: C,
61.73; H, 4.73.
(Z)-1-Benzoyl-1-(4-methylphenyl)thio-3-methoxy-
propene 3i. Oil. IR (film): ν (cm−1) 2927, 1667,
1597, 1592, 1448, 1403, 1094, 808, 716; 1H NMR
(400 MHz, CDCl3): δ 7.72 (d, J = 8.4 Hz, 2H),
7.51–7.35 (m, 3H), 7.16 (d, J = 8.0 Hz, 2H), 6.99
(d, J = 8.0 Hz, 2H), 6.59 (t, J = 5.6 Hz, 1H), 4.40
(d, J = 5.6 Hz, 2H), 3.43 (s, 3H), 2.24 (s, 3H); 13C
NMR (100 MHz, CDCl3): δ 193.08, 141.84, 137.57,
136.79, 133.46, 132.71, 131.33, 129.83, 129.54,
129.15, 128.23, 70.01, 58.75, 21.05; MS (EI, 70 eV):
m/z 298 (M+, 54), 267 (66), 105 (100); Anal. calcd
for C18H18O2S: C, 72.47; H, 6.08. Found: C, 72.64; H,
6.25.
(Z)-1-Benzoyl-1-phenylthio-3-methoxypropene
3e. Oil. IR (film): ν (cm−1) 3060, 2929, 1667, 1597,
1580, 1448, 1248, 1100, 745, 690; 1H NMR (400
MHz, CDCl3): δ 7.73 (d, J = 8.0 Hz, 2H), 7.53–7.34
(m, 3H), 7.27–7.14 (m, 5H), 6.69 (t, J = 5.6 Hz, 1H),
4.40 (d, J = 5.6 Hz, 2H), 3.43 (s, 3H); 13C NMR
(100 MHz, CDCl3): δ 192.97, 143.20, 136.87, 136.73,
133.08, 132.72, 130.70, 129.46, 129.06, 128.26,
127.29, 70.08, 58.79; MS (EI, 70 eV): m/z 284 (M+,
41), 253 (100), 144 (36), 109 (41), 105 (87); Anal.
calcd for C17H16O2S: C, 71.82; H, 5.67. Found: C,
71.55; H, 5.79.
(Z)-1-Benzoyl-1-phenylthio-2-phenylethene
3j.
(Z)-1-(4-Methylbenzoyl)-1-phenylthio-3-methoxy-
White solid. Mp. 75–76◦C (lit. [36] Mp. 74–75◦C). IR
propene 3f. Oil. IR (film): ν (cm−1) 3061, 2928,
(KBr): ν (cm−1) 3060, 1667, 1581, 1447, 1241, 745,
1
1666, 1596, 1583, 1447, 1249, 1101, 690; H NMR
1
690; H NMR (400 MHz, CDCl3): δ 7.80 (d, J = 7.6
(400 MHz, CDCl3): δ 7.67 (d, J = 8.0 Hz, 2H),
7.28–7.24 (m, 3H), 7.21–7.15 (m, 4H), 6.64 (t, J =
5.6 Hz, 1H), 4.39 (d, J = 5.6 Hz, 2H), 3.42 (s, 3H),
2.38 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 192.63,
143.67, 142.47, 136.87, 134.01, 133.16, 130.66,
129.72, 129.24, 128.99, 127.23, 70.03, 58.73, 21.66;
MS (EI, 70 eV): m/z 298 (M+, 6.8), 296 (100), 282
(85), 253 (34), 239 (40), 105 (58), 91 (62); Anal. calcd
for C18H18O2S: C, 72.47; H, 6.08. Found: C, 72.19; H,
5.87.
Hz, 2H), 7.73 (d, J = 8.4 Hz, 2H), 7.50–7.34 (m,
6H), 7.27–7.11 (m, 6H); 13C NMR (100 MHz, CDCl3):
δ 194.47, 139.87, 137.38, 135.58, 134.63, 133.08,
132.50, 131.29, 130.42, 129.45, 128.96, 128.56,
128.48, 128.12, 127.38; MS (EI, 70 eV): m/z 316 (M+,
8.3), 211 (17), 109 (34), 105 (100); Anal. calcd for
C21H16OS: C, 79.73; H, 5.10. Found: C, 79.54; H,
5.23%.
(Z)-1-(4-Chlorobenzoyl)-1-(4-chlorophenyl)thio-
2-phenylethene 3k. White solid. Mp. 81–83◦C. IR
(KBr): ν (cm−1) 2925, 1665, 1587, 1475, 1092, 819,
(Z)-1-(4-Chlorobenzoyl)-1-phenylthio-3-methoxy-
propene 3g. Oil. IR (film): ν (cm−1) 2929, 1669,
1
762; H NMR (400 MHz, CDCl3): δ 7.80–7.76 (m,
1
1593, 1580, 1402, 1093, 691; H NMR (400 MHz,
2H), 7.68 (d, J = 8.4 Hz, 2H), 7.47–7.31 (m, 5H),
7.24–7.13 (m, 5H); 13C NMR (100 MHz, CDCl3):
δ 192.98, 140.42, 139.09, 137.18, 135.47, 134.51,
134.23, 133.43, 132.55, 130.92, 130.74, 130.45,
129.22, 129.03, 128.57; MS (EI, 70 eV): m/z 384 (M+,
35Cl, 39), 139 (45), 111 (66), 109 (100); Anal. calcd
for C21H14OSCl2: C, 65.63; H, 3.67. Found: C, 65.41;
H, 3.85.
CDCl3): δ 7.49 (d, J = 8.4 Hz, 2H), 7.19 (d, J = 8.4
Hz, 2H), 7.15–7.13 (m, 5H), 6.43 (t, J = 5.6 Hz,
1H), 4.39 (d, J = 5.6 Hz, 2H), 3.43 (s, 3H); 13C
NMR (100 MHz, CDCl3): δ 193.27, 134.93, 134.33,
130.65, 129.44, 129.01, 128.94, 128.87, 128.69,
128.42, 126.18, 70.71, 58.48; MS (EI, 70 eV): m/z
318 (M+, 35Cl, 1.4), 259 (26), 123 (55), 111 (64), 109
(100); Anal. calcd for C17H15O2SCl: C, 64.05; H, 4.74.
Found: C, 63.77; H, 4.49.
REFERENCES
(Z)-1-(4-Nitrobenzoyl)-1-phenylthio-3-methoxy-
propene 3h. Oil. IR (film): ν (cm−1) 2928, 1672,
1595, 1521, 1404, 1346, 1093, 690; 1H NMR
(400 MHz, CDCl3): δ 8.08 (d, J = 8.8 Hz, 2H), 7.70
(d, J = 8.8 Hz, 2H), 7.16–7.07 (m, 5H), 6.56 (t, J
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