An economical and convenient synthesis of vinyl sulfones

Article abstract of DOI:10.1055/s-2007-966039

A general process for the efficient synthesis of vinyl sulfones has been developed using commercially available sulfinic acid sodium salts and dibromides. A variety of phenyl and methyl vinyl sulfones have been formed in good yields, in the absence of any catalyst. Georg Thieme Verlag Stuttgart.

Full text of DOI:10.1055/s-2007-966039

PAPER
1465
An Economical and Convenient Synthesis of Vinyl Sulfones
An
E
conomical
h
and Conven
e
ient Synthe
n
sis of
V
inyl
S
ulfone
s
-Hui Guan, Wei Zuo, Lian-Biao Zhao, Zhi-Hui Ren, Yong-Min Liang*
State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, P. R. of China
Fax +86(931)8912582; E-mail: liangym@lzu.edu.cn
Received 7 February 2007; revised 16 March 2007
We have reported the stereoselective synthesis of (Z)-b-
chlorovinyl sulfones by the addition of sulfonyl chlorides
to acetylenes.8a However, the key to the success of the re-
action lies in the use of copper(I) chloride as catalyst and
dimethyl sulfide as an additive. Recently, we found that
the reaction of sulfinic acid sodium salts and dibromides
could be carried out at 80 °C in N,N-dimethylformamide
(DMF) to give the corresponding vinyl sulfones directly
in good yields (Scheme 1). Herein we wish to describe in
detail these results.
Abstract: A general process for the efficient synthesis of vinyl sul-
fones has been developed using commercially available sulfinic
acid sodium salts and dibromides. A variety of phenyl and methyl
vinyl sulfones have been formed in good yields, in the absence of
any catalyst.
Key words: vinyl sulfones, sulfinic acid sodium salts, dibromides,
synthesis
It is well known that vinyl sulfones have wide applica-
tions in organic synthesis.1 The activating and electron-
withdrawing effects of the sulfone moiety enable these
compounds to undergo highly stereoselective conjugate
additions and cycloadditions.2 Furthermore, the sulfone
group can be removed at the end of a synthetic sequence
by a variety of reductive, alkylative or oxidative methods,
where the sulfone moiety is replaced by a hydrogen or an
alkyl group generated from a suitable organometallic
cross-coupling reagent or an oxygen function, respective-
ly.3 Vinyl sulfones in medicinal chemistry, on the other
hand, represent a new class of small-molecule electro-
philic inactivators of cysteine proteases.4 They have also
recently been shown to act as inhibitors of SrtA, a
transpeptidase required for protein anchoring to the cell
wall and virulence in Staphylococcus aureus.5
O
R1
O
S
R1
DMF
S
+
Br
R2
ONa
80 °C
O
Br
R2
1
2
3
R1 = CONH2, CO2Me, CN, CO2H, CHO, Me, Ph, etc.
2 = Ph or Me
R
Scheme 1
Our experiment was first conducted by treating 2,3-dibro-
mopropanamide (1a) with sodium phenylsulfinate dihy-
drate (2a; Table 1). The reaction proceeded well and
produced (E)-3-(phenylsulfonyl)acrylamide (3aa) at
80 °C in DMF in 72% yield (entry 1). Higher yields were
obtained by prolonging the reaction time (entries 2 and 3).
Among the solvents tested, DMF gave the best result, with
Conventionally, protocols for the preparation of vinyl sul-
fones mainly consist of (a) oxidation of the corresponding
b-arylthio systems and b-elimination6 (b) ionic or radical
addition of PhSO2X (X = Cl, Br, I, SePh, etc.) to alkenes
followed by b-elimination,7 or to alkynes8 (c) Horner–
Emmons reaction of carbonyl compounds and sulfonyl
phosphoranes9 (d) hydrozirconation reaction of 1-alkynyl
sulfones10 or selenosulfonation of acetylene11(e) palladi-
um-catalyzed cross-coupling reactions12 (f) cross-meta-
thesis of vinyl sulfones with terminal olefins.13 Although
these protocols provide access to vinyl sulfones, they suf-
fer from either harsh reaction conditions or from the high
costs of the metal reagents and/or the corresponding
ligands. None of these methods are simple, nor can they
be usefully applied for the generation of functionally sub-
stituted vinyl sulfones. Thus, the development of efficient
and highly stereoselective methodologies for the synthe-
sis of vinyl sulfones is of current interest.14
Table 1 Formation of 3aa under a Range of Conditionsa
Entry
Solvent
DMF
Time (h)
Isolated yield (%)
1
2
3
4
5
6
7
8
9
8
12
20
12
12
12
12
12
12
72
80
81
47
53
59b
43
26
52
DMF
DMF
DMSO
DMA
THF
MeCN
EtOH
Toluene
a Reagents and conditions: 2,3-dibromopropanamide (1a; 0.5 mmol),
sodium phenylsulfinate dihydrate (2a; 0.75 mmol), 80 °C in given
solvent (1.0 mL).
SYNTHESIS 2007, No. 10, pp 1465–1470
Advanced online publication: 02.05.2007
DOI: 10.1055/s-2007-966039; Art ID: F03007SS
x
x.
x
x
.
2
0
0
7
b Reaction was carried out at 60 °C.
© Georg Thieme Verlag Stuttgart · New York

1466
Z.-H. Guan et al.
PAPER
the use of alternative solvents failing to improve the yield such as amide, ketone, ester, acid and nitrile were all suit-
of product (entries 4–9).
able for this reaction, giving the desired products in good
yields (entries 1–4, 6, 7). It is noteworthy that the reaction
of 2,3-dibromopropanal (1e) could be carried out at room
temperature to give (E)-3-(phenylsulfonyl)acrylaldehyde
This promising result encouraged us to explore the gener-
ality of this reaction. The results are summarized in
Table 2. It was found that a wide variety of dibromides,
Table 2 Synthesis of Phenyl Vinyl Sulfones from Sodium Phenylsulfinate Dihydrate (2a) and Dibromides 1
Entry
1
Dibromide 1
Product 3a
Time (h)
12
Isolated yield (%)
80
1a
1b
1c
1d
1e
1f
3aa
3ab
3ac
3ad
3ae
3af
O
NH2
Br
O
O
O
O
O
S
NH2
O
Ph
Br
2
3
4
5
6
7
7
86
88
86
76a
82
O
O
S
Br
O
Ph
Br
O
OMe
Br
O
S
OMe
OEt
O
Ph
Br
10
20
10
O
OEt
Br
O
S
O
Ph
Br
O
O
O
O
S
H
H
Br
O
Ph
Br
O
OH
Br
O
S
OH
O
Ph
Br
7
8
9
1g
1h
1i
3ag
3ah
3ai
10
24
10
80
78
75
CN
O
S
CN
Br
Br
O
Br
Br
Ph
O
S
O
Ph
O
S
Ph
O
O
Ph
O
Br
Ph
Br
10
11
12
1j
1k
1l
3aja
3ajb
6
12
10
70
O
S
(5:1)b
Br
O
Br
Ph
O
S
O
Ph
3aka
3akb
66
O
S
C5H11
C5H11
(5:1)b
Br
O
Ph
Br
C5H11
O
S
O
Ph
3al
65c
O
S
Ph
Ph
Br
O
Ph
Br
a Reaction was carried out at r.t.
b Ratio based on 1H NMR.
c Using Et3N (0.75 mmol) as base, HMPA (1.0 mL) as solvent.
Synthesis 2007, No. 10, 1465–1470 © Thieme Stuttgart · New York

PAPER
An Economical and Convenient Synthesis of Vinyl Sulfones
1467
R1
Br
R1
R1
R2
(3ae) in 76% yield (entry 5). Dibromoalkanes also per-
formed well in this process to afford vinyl sulfones in
good yields (entries 8–11). When 1,2-dibromopropane
(1j) and 1,2-dibromoheptane (1k) were treated with sodi-
um phenylsulfinate dihydrate (2a), the reaction resulted in
a mixture of 1-(1-vinylsulfonyl)benzene- and 1-(2-vinyl-
sulfonyl)benzene-substituted products in 5:1 ratios (en-
tries 10 and 11).15a For 1-phenyl-1,2-dibromoethane (1l),
the reaction gave a mixture of products under the above
conditions; however, when hexamethylphosphoramide
(HMPA) was used as solvent and triethylamine as base,
the 1-[(E)-styrylsulfonyl]benzene was obtained in 65%
yield (entry 12).
R2SO2
R2SO2
Br
SO2
Br
Br
O
1
4
5
R1
R1
O2
S
R2SO2
R2SO2H
R2
S
R2
O
S
R2
O2
6
3
Scheme 2
In summary, we have developed a mild, efficient and
metal-free method for the synthesis of vinyl sulfones,
which employs inexpensive and readily available starting
materials. The method is simple and tolerates of a wide
variety of functional groups, thus providing a general
route to vinyl sulfones.
As methyl vinyl sulfones are also compounds of interest,
a few examples using commercially available methane-
sulfinic acid sodium salt (2b) were performed. As de-
scribed in Table 3, these trials also gave satisfactory
yields. It is worth noting that the addition of a small
amount of water could improve the reaction efficiency;
this is presumably due to the increased water solubility of
the methanesulfinic acid sodium salt (2b). These exam-
ples, in particular, demonstrate the superiority of the
present approach to forming methyl vinyl sulfones over
previously described methods since, using the conditions
detailed here, otherwise harsh reaction conditions and
complex operational processes can be avoided.
All reagents and solvents were pure, analytical grade materials pur-
chased from commercial sources and were used without further pu-
rification, unless otherwise stated. Dibromides were prepared by
addition of Br2 to olefins.16 All melting points are uncorrected. H
1
NMR spectra were recorded at 300 MHz and 13C NMR spectra were
recorded at 75 MHz in CDCl3, DMSO-d6 or D2O using TMS as in-
ternal standard on a Varian Mercury Plus 300BB spectrometer. IR
spectra were obtained on a Nicolet AVATAR 360 FT-IR spectrome-
ter. Mass spectra were recorded by the EI (70 eV) method on a
HP5998 MS spectrometer. Microanalyses were performed on a
Vario EL instrument. TLC was carried out using 0.2 mm thick silica
gel plates (GF254) and visualized under UV light. The columns
were hand-packed with silica gel (200–300 mesh, Qingdao Haiyang
Chemical Co., Ltd.). All reactions were carried out in 5 mL flasks
equipped with a magnetic stir bar.
Table 3 Synthesis of Methyl Vinyl Sulfones from Methanesulfinic
Acid Sodium Salt (2b) and Dibromides 1a
Entry Dibromide 1
Product 3b
Isolated
yield (%)
O
O
O
O
Synthesis of Phenyl Vinyl Sulfones; General Procedure
A mixture of sodium phenylsulfinate dihydrate (0.75 mmol), the di-
bromide (0.5 mmol) and DMF (1 mL) was added to a 5 mL flask
equipped with a magnetic stir bar and the mixture was stirred at
80 °C for 12 h. After cooling to r.t. the reaction mixture was treated
with H2O (3 mL) and extracted with EtOAc (3 × 2 mL). The com-
bined organic layers were washed with brine (3 mL), dried over
Na2SO4, filtered and concentrated under reduced pressure. The
product was further purified by column chromatography (hexanes–
EtOAc, 10:1).
O
S
NH2
1
1a
1d
3ba 81
NH2
OEt
OH
Br
O
Me
Br
O
O
S
OEt
2
3bb 75
Br
O
Me
Br
O
O
S
OH
3
1f
3bc 86
3bd 80
Br
O
Me
(E)-3-(Phenylsulfonyl)acrylamide (3aa)
Br
Colorless crystals; mp 159–160 °C (Lit.17 159–160 °C).
O
S
CN
CN
4
1g
IR (KBr): 3431, 3322, 1679, 1446, 1377 cm–1.
Br
O
Me
Br
1H NMR (300 MHz, DMSO-d6): d = 6.98 (d, J = 15.3 Hz, 1 H),
7.46 (d, J = 15.3 Hz, 1 H), 7.64–7.79 (m, 4 H), 7.90–7.93 (m, 2 H),
8.06 (s, 1 H).
a Reagents and conditions: dibromide (1; 0.5 mmol), methanesulfinic
acid sodium salt (2b; 0.6 mmol), 80 °C in 1.0 mL DMF–H2O (4:1), 10
h.
13C NMR (75 MHz, DMSO-d6): d = 127.8 (2C), 129.8 (2C), 134.4,
135.4, 138.9, 139.1, 163.1.
MS (EI): m/z = 211 [M+], 146, 141, 125.
A tentative mechanism for the formation of vinyl sulfones
is proposed in Scheme 2. Dehydrobromination of dibro-
mides 1 is effected by the sulfinate anion to give 4, to
which conjugate addition of a sulfinate anion occurs to af-
ford 5. The remaining bromine atom in 5 is then substitut-
ed by a sulfinate anion to give 6, from which sulfinic acid
elimination affords the vinyl sulfones 3.15
Anal. Calcd for C9H9NO3S: C, 51.17; H, 4.29; N, 6.63. Found: C,
51.09; H, 4.32; N, 6.81.
(E)-4-(Phenylsulfonyl)but-3-en-2-one (3ab)
Colorless crystals; mp 59–60 °C (Lit.18 61–62.5 °C).
IR (KBr): 3042, 1699, 1449, 1314, 1084 cm–1.
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1468
Z.-H. Guan et al.
PAPER
1H NMR (300 MHz, CDCl3): d = 2.37 (s, 3 H), 7.02 (d, J = 15.3 Hz,
1 H), 7.16 (d, J = 15.3 Hz, 1 H), 7.58–7.63 (m, 2 H), 7.68–7.71 (m,
1 H), 7.91–7.94 (m, 2 H).
13C NMR (75 MHz, CDCl3): d = 28.3, 128.2 (2C), 129.6 (2C),
134.4, 135.9, 138.2, 140.8, 195.6.
(E)-3-(Phenylsulfonyl)acrylonitrile (3ag)
Colorless crystals; mp 103–104 °C (Lit.17 103–104 °C).
IR (KBr): 3061, 2923, 1149, 1082 cm–1.
1H NMR (300 MHz, CDCl3): d = 6.56 (d, J = 15.9 Hz, 1 H), 7.24 (d,
J = 15.9 Hz, 1 H), 7.10–7.66 (m, 2 H), 7.73–7.78 (m, 1 H), 7.79–
7.93 (m, 2 H).
MS (EI): m/z = 210 [M+], 195, 125.
Anal. Calcd for C10H10O3S: C, 57.13; H, 4.79. Found: C, 57.12; H,
4.66.
13C NMR (75 MHz, CDCl3): d = 110.6, 113.3, 128.5 (2C), 129.9
(2C), 135.1, 137.1, 148.9.
MS (EI): m/z = 193 [M+], 167, 151, 141.
Methyl (E)-3-(Phenylsulfonyl)acrylate (3ac)
Colorless crystals; mp 98–99 °C (Lit.18 97.5–100 °C).
Anal. Calcd for C9H7NO2S: C, 55.94; H, 3.65; N, 7.25. Found: C,
55.96; H, 3.56; N, 7.04.
IR (KBr): 3066, 1722, 1307, 1085 cm–1.
1H NMR (300 MHz, CDCl3): d = 3.78 (s, 3 H), 6.83 (d, J = 15.3 Hz,
1 H), 7.33 (d, J = 15.3 Hz, 1 H), 7.55–7.60 (m, 2 H), 7.66–7.69 (m,
1 H), 7.89–7.92 (m, 2 H).
13C NMR (75 MHz, CDCl3): d = 52.8, 128.3 (2C), 129.6 (2C),
130.4, 134.4, 138.2, 143.3, 163.8.
1-(Vinylsulfonyl)benzene (3ah)
Colorless crystals; mp 66–68 °C (Lit.18 66.5–68.5 °C).
IR (KBr): 2924, 2854, 1377, 1147 cm–1.
1H NMR (300 MHz, CDCl3): d = 6.06 (d, J = 10.2 Hz, 1 H), 6.48 (d,
J = 16.2 Hz, 1 H), 6.63–6.72 (m, 1 H), 7.54–7.59 (m, 2 H), 7.63–
7.68 (m, 1 H), 7.89–7.92 (m, 2 H).
MS (EI): m/z = 226 [M+], 195, 125.
Anal. Calcd for C10H10O4S: C, 53.09; H, 4.46. Found: C, 53.27; H,
4.29.
13C NMR (75 MHz, CDCl3): d = 127.8, 127.9 (2C), 129.3 (2C),
133.6 (2C), 138.3.
MS (EI): m/z = 168 [M+], 125, 77.
Ethyl (E)-3-(Phenylsulfonyl)acrylate (3ad)
Colorless oil.
IR (KBr): 3064, 2985, 1448, 1148, 1029 cm–1.
Anal. Calcd for C8H8O2S: C, 57.12; H, 4.79. Found: C, 57.37; H,
4.96.
1H NMR (300 MHz, CDCl3): d = 1.31 (t, J = 7.2 Hz, 3 H), 4.25 (q,
J = 7.2 Hz, 2 H), 6.85 (d, J = 15.3 Hz, 1 H), 7.35 (d, J = 15.3 Hz,
1 H), 7.58–7.63 (m, 2 H), 7.68–7.30 (m, 1 H), 7.92–7.95 (m, 2 H).
13C NMR(75 MHz, CDCl3): d = 13.9, 61.9, 128.2 (2C), 129.5 (2C),
130.9, 134.3, 138.2, 142.9, 163.3.
1-[(E)-3-(Benzyloxy)prop-1-enylsulfonyl]benzene (3ai)
Colorless crystals; mp 129–131 °C.
IR (KBr): 3443, 2920, 1305, 1149, 1083 cm–1.
1H NMR (300 MHz, CDCl3): d = 4.20–4.22 (m, 2 H), 4.54 (s, 2 H),
6.68 (d, J = 15.3 Hz, 1 H), 7.00 (d, J = 15.0, 1 H), 7.30–7.34 (m,
5 H), 7.50–7.56 (m, 2 H), 7.59–7.62 (m, 1 H), 7.87–7.90 (m, 2 H).
MS (EI): m/z = 240 [M+], 195, 141, 125.
Anal. Calcd for C11H12O4S: C, 54.99; H, 5.03. Found: C, 55.10; H,
5.19.
13C NMR (75 MHz, CDCl3): d = 67.5, 73.1, 127.6 (4C), 127.9,
128.5 (2C), 129.2 (2C), 130.2, 133.3, 137.0, 140.1, 142.4.
MS (EI): m/z = 259, 232, 182, 167, 91.
(E)-3-(Phenylsulfonyl)acrylaldehyde (3ae)
Colorless crystals; mp 49–50 °C.
IR (KBr): 3441, 2838, 1448, 1151, 1080 cm–1.
Anal. Calcd for C16H16O3S: C, 66.64; H, 5.59. Found: C, 66.88; H,
5.73
1H NMR (300 MHz, CDCl3): d = 6.88–6.95 (m, 1 H), 7.26 (d,
J = 15.3 Hz, 1 H), 7.60–7.65 (m, 2 H), 7.71–7.76 (m, 1 H), 7.94–
7.97 (m, 2 H), 9.74 (d, J = 7.2 Hz, 1 H).
13C NMR (75 MHz, CDCl3): d = 128.5 (2C), 129.8 (2C), 134.7,
136.2, 137.8, 147.8, 189.7.
1-[(E)-Prop-1-enylsulfonyl]benzene (3aja)
IR (KBr): 3066, 1641, 1306, 1085 cm–1.
1H NMR (300 MHz, CDCl3): d = 1.91–1.97 (m, 3 H), 6.36 (d,
J = 14.7 Hz, 1 H), 6.96–7.03 (m, 1 H), 7.51–7.65 (m, 3 H), 7.87–
7.91 (m, 2 H).
MS (EI): m/z = 196 [M+], 141, 125.
13C NMR (75 MHz, CDCl3): d = 17.3, 127.5 (2C), 129.2 (2C),
131.6, 133.2, 140.5, 142.5.
Anal. Calcd for C9H8O3S: C, 55.09; H, 4.11. Found: C, 54.85; H,
4.00.
MS (EI): m/z = 182 [M+], 125, 77.
Anal. Calcd for C9H10O2S: C, 59.32; H, 5.53. Found: C, 59.35; H,
5.25.
(E)-3-(Phenylsulfonyl)acrylic Acid (3af)
Colorless crystals; mp 130–131 °C.
IR (KBr): 3070, 2919, 2568, 1700, 1082 cm–1.
1-[(E)-Hept-1-enylsulfonyl]benzene (3aka)
Colorless oil.
IR (KBr): 2957, 2860, 1447, 1086 cm–1.
1H NMR (300 MHz, CDCl3): d = 0.83–0.89 (m, 3 H), 1.21–1.30 (m,
4 H), 1.42–1.49 (m, 2 H), 2.20–2.27 (m, 2 H), 6. 32 (d, J = 15.0 Hz,
1 H), 6.96–7.03 (m, 1 H), 7.52–7.62 (m, 3 H), 7.87–7.90 (m, 2 H).
1H NMR (300 MHz, CDCl3): d = 6.83 (d, J = 15.3 Hz, 1 H), 7.43 (d,
J = 15.3 Hz, 1 H), 7.58–7.63 (m, 2 H), 7.69–7.74 (m, 1 H), 7.92–
7.95 (m, 2 H), 10.68 (br s, 1 H).
13C NMR (75 MHz, CDCl3): d = 128.4 (2C), 129.7 (2C), 129.8,
134.6, 137.9, 145.1, 168.1.
MS (EI): m/z = 212 [M+], 166, 149, 125.
13C NMR (75 MHz, CDCl3): d = 13.8, 22.2, 27.2, 31.1, 31.3, 127.4
(2C), 129.1, 129.2, 130.1, 133.2, 140.5, 147.3.
Anal. Calcd for C9H8O4S: C, 50.94; H, 3.80. Found: C, 51.05; H,
3.59.
MS (EI): m/z = 238 [M+], 183, 169, 143.
Anal. Calcd for C13H18O2S: C, 65.51; H, 7.61. Found: C, 65.32; H,
7.43.
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PAPER
An Economical and Convenient Synthesis of Vinyl Sulfones
1469
1-[(E)-Styrylsulfonyl]benzene (3al)
13C NMR (75 MHz, CDCl3): d = 42.3, 113.1, 147.6 (2C).
MS (EI): m/z = 131 [M+], 105, 69, 63, 32.
Colorless crystals; mp 70–71 °C (Lit.7c 70–71 °C).
IR (KBr): 3049, 1613, 1446, 1084 cm–1.
1H NMR (300 MHz, CDCl3): d = 6.87 (d, J = 15.3 Hz, 1 H), 7.36–
7.62 (m, 8 H), 7.69 (d, J = 15.3, 1 H), 7.94–7.97 (m, 2 H).
Anal. Calcd for C4H5NO2S: C, 36.63; H, 3.84; N, 10.68. Found: C,
36.59; H, 3.58; N, 10.62.
13C NMR (75 MHz, CDCl3): d = 127.3, 127.6 (2C), 128.5 (2C),
129.1 (2C), 129.3 (2C), 131.2, 132.3, 133.3, 140.7, 142.5.
Acknowledgment
The authors thank the NSFC (NSFC-20621091) for financial sup-
port.
MS (EI): m/z 244 [M+], 190, 179, 141.
Anal. Calcd for C14H12O2S: C, 68.83; H, 4.95. Found: C, 68.58; H,
4.90.
References
Synthesis of Methyl Vinyl Sulfones; General Procedure
To a mixture of methanesulfinic acid sodium salt (0.6 mmol), dibro-
mide (0.5 mmol) and DMF–H2O (4:1; 1 mL) was added to a 5 mL
flask equipped with a magnetic stir bar and the mixture was stirred
at 80 °C for 10 h. After cooling to r.t., the reaction mixture was
treated with H2O (3 mL) and extracted with EtOAc (3 × 2 mL). The
combined organic layers were washed with brine (3 mL), dried over
Na2SO4, filtered and concentrated under reduced pressure. The
product was further purified by column chromatography (hexanes–
EtOAc, 6:1).
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Chem. 1998, 6, 2477. (l) Alonso, I.; Carretero, J. C.;
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7973.
(E)-3-(Methylsulfonyl)acrylamide (3ba)
Colorless crystals; mp 138–140 °C.
IR (KBr): 3437, 3067, 1675, 1404, 1132 cm–1.
1H NMR (300 MHz, D2O): d = 3.06 (s, 3 H), 6.90 (d, J = 15.3 Hz,
1 H), 7.33 (d, J = 15.3 Hz, 1 H).
13C NMR (75 MHz, D2O); d = 41.5, 135.5, 138.5, 166.5.
MS (EI): m/z = 149 [M+], 105, 87, 63, 32.
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1999, 55, 10547.
Anal. Calcd for C4H7NO3S: C, 32.21; H, 4.73; N, 9.39. Found: C,
32.34; H, 4.47; N, 9.58.
Ethyl (E)-3-(Methylsulfonyl)acrylate (3bb)
Colorless crystals; mp 62.5–63 °C.
IR (KBr): 3058, 2986, 1711, 1472, 1031 cm–1.
1H NMR (300 MHz, CDCl3): d = 1.32–1.37 (m, 3 H), 3.03 (s, 3 H),
4.30 (q, J = 7.2 Hz, 2 H), 6.87 (d, J = 15.3 Hz, 1 H), 7.40 (d,
J = 15.3 Hz, 1 H).
13C NMR (75 MHz, CDCl3): d = 14.0, 42.4, 62.2, 132.9, 141.7,
163.2.
MS (EI): m/z = 178 [M+], 133, 99, 71, 63.
Anal. Calcd for C6H10O4S: C, 40.44; H, 5.66. Found: C, 40.22; H,
5.41.
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(E)-3-(Methylsulfonyl)acrylic Acid (3bc)
Colorless crystals; mp 101–103 °C.
IR (KBr): 3066, 2670, 1698, 1421, 1132 cm–1.
1H NMR (300 MHz, D2O): d = 3.05 (s, 3 H), 6.73 (d, J = 15.0 Hz,
1 H), 7. 41 (d, J = 15.3 Hz, 1 H).
13C NMR (75 MHz, D2O): d = 41.4, 134.0, 140.7, 166.9.
MS (EI): m/z = 149 [M+ – 1], 135, 88, 71, 63, 45.
G. J. Am. Chem. Soc. 2004, 126, 3404.
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Goumont, R.; Magder, K.; Wakselman, C. J. Fluorine
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N. O. J. Org. Chem. 1993, 58, 4506.
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(b) Liu, L. K.; Chi, Y.; Jen, K. Y. J. Org. Chem. 1980, 45,
406. (c) Nair, V.; Augustine, A.; Suja, T. D. Synthesis 2002,
2259. (d) Zhu, S.; Qin, C.; Xu, G.; Chu, Q. Tetrahedron Lett.
1998, 39, 5265. (e) Nair, V.; Augustine, A.; George, T. G.;
Nair, L. G. Tetrahedron Lett. 2001, 42, 6763. (f)Nájera,G.;
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Anal. Calcd for C4H6O4S: C, 32.00; H, 4.03. Found: C, 32.14; H,
3.91.
(E)-3-(Methylsulfonyl)acrylonitrile (3bd)
Colorless crystals; mp 103.5–104.5 °C.
IR (KBr): 3070, 2926, 1710, 1409, 1140 cm–1.
1H NMR (300 MHz, CDCl3): d = 3.07 (s, 3 H), 6.59 (d, J = 15.3 Hz,
1 H), 7.33 (d, J = 15.3 Hz, 1 H).
Synthesis 2007, No. 10, 1465–1470 © Thieme Stuttgart · New York

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Synthesis 2007, No. 10, 1465–1470 © Thieme Stuttgart · New York