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RSC Advances
(E)-1-methyl-2-(2-(phenylsulfonyl)vinyl)benzene (3c): Eluent
NMR (CDCl3, 400 MHz, ppm) δ 7.84 (d, 2H, J = 8 Hz), 7.62 (d,
petroleum ether/ethyl acetate (10:1), white solid, mp = 112−115
1H, J = 16 Hz), 7.43 (d, 2H, J = 8 Hz), 7.39-7.36 (m, 4H), 6.85 (d,
°C. 1H NMR (CDCl3, 400 MHz, ppm) δ 7.98-7.93 (m, 3H), 7.61- 60 1H, J = 16 Hz), 2.46 (s, 3H). 13C NMR (CDCl3, 100 MVHiezw, Aprpticmle)Oδnline
DOI: 10.1039/C5RA02927A
7.59 (m, 1H), 7.56-7.52 (m, 2H), 7.42 (d, 1H, J = 8.0 Hz), 7.27
(dd, 1H, J = 8.0 Hz), 7.21-7.27 (m, 2H), 6.78 (d, 1H, J = 16 Hz),
2.44 (s, 3H). 13C NMR (CDCl3, 100 MHz, ppm) δ 140.8, 140.2,
138.3, 133.4, 131.4, 131.1, 131.0, 129.4, 128.3, 127.7, 127.0,
126.6, 19.8. ESI-MS [M+H]+ m/z 259.1.
144.6, 140.4, 137.5, 137.2, 131.0, 130.0, 129.7, 129.4, 128.3,
5
127.8, 21.6. ESI-MS [M+H]+ m/z 294.2.
(E)-1-chloro-4-(styrylsulfonyl)benzene
(3k):[1]
Eluent
petroleum ether/ethyl acetate (10:1), pale yellow solid, mp =
65 85−87 °C. 1H NMR (CDCl3, 400 MHz, ppm) δ 7.91 (d, 2H, J = 8
Hz), 7.71 (d, 1H, J = 16 Hz), 7.56-7.52 (m, 4H), 7.45-7.42 (m,
3H), 6.86 (d, 1H, J = 16 Hz). 13C NMR (CDCl3, 100 MHz, ppm)
δ 143.1, 140.1, 139.3, 132.2, 131.4, 129.7, 129.2, 128.7, 126.9,
125.7. HRMS m/z calcd. for C14H12ClO2S [M+H]+: 279.0247,
(E)-1-fluoro-4-(2-(phenylsulfonyl)vinyl)benzene (3d): Eluent
10 petroleum ether/ethyl acetate (10:1). pale yellow solid, mp = 110-
112 °C. 1H NMR (CDCl3, 400 MHz, ppm) δ 7.97 (d, 2H, J = 8.0
Hz), 7.68 (d, 1H, J = 16 Hz), 7.63 (d, 1H, J = 8.0 Hz), 7.60-7.56
(m, 2H), 7.53-7.49 (m, 2H), 7.11 (t, 2H, J = 8.0 Hz), 6.81 (d, 1H, 70 found: 279.0238.
J = 16 Hz). 13C NMR (CDCl3, 100 MHz, ppm) δ 166.6, 163.1,
15 140.3 (d, J = 100.1 Hz), 133.5, 130.5 (d, J = 18.2 Hz), 129.4,
128.6 (d, J = 6.0 Hz), 127.7, 127.1 (d, J = 6.0 Hz), 116.5, 116.2.
ESI-MS [M+H]+ m/z 263.2.
(E)-1-(2-(4-chlorophenylsulfonyl)vinyl)-3-methylbenzene (3l):
Eluent petroleum ether/ethyl acetate (10:1), colorless oil. 1H
NMR (CDCl3, 400 MHz, ppm) δ 7.86 (d, 2H, J = 4 Hz), 7.62 (d,
1H, J = 12 Hz), 7.50 (d, 2H, J = 4 Hz), 7.28-7.21 (m, 4H), 6.80 (d,
(E)-1-chloro-4-(2-(phenylsulfonyl)vinyl)benzene (3e):[3] Eluent 75 1H, J = 12 Hz), 2.35 (s, 3H). 13C NMR (CDCl3, 100 MHz, ppm)
petroleum ether/ethyl acetate (10:1). colorless solid, mp =
20 127−129 °C. 1H NMR (CDCl3, 400 MHz, ppm) δ 7.97 (d, 2H, J =
8.0 Hz), 7.67 (d, 1H, J = 16 Hz), 7.60-7.56 (m, 3H), 7.44 (d, 2H,
J = 8 Hz), 7.38 (d, 2H, J = 8 Hz), 6.87 (d, 1H, J = 16 Hz). 13C
NMR (CDCl3, 100 MHz, ppm) δ 141.0, 140.7, 137.3, 133.5,
130.9, 129.8, 129.4, 128.9, 127.9, 127.7. ESI-MS [M+H]+ m/z
25 279.2.
δ 143.4, 140.2, 139.4, 139.0, 132.3, 132.2, 129.7, 129.3, 129.2,
129.1, 126.7, 126.0, 21.3. ESI-MS [M+H]+ m/z 294.2.
(E)-1-chloro-4-(2-(4-chlorophenylsulfonyl)vinyl)benzene (3m):
Eluent petroleum ether/ethyl acetate (10:1), pale yellow solid, mp
80 = 164−166 °C. 1H NMR (CDCl3, 400 MHz, ppm) δ 7.90 (d, 2H, J
= 8 Hz), 7.64 (d, 1H, J = 16 Hz), 7.56 (d, 2H, J = 8 Hz), 7.51-
7.49 (m, 1H, 7.42-7.37 (m, 3H), 6.87 (d, 1H, J = 16 Hz). 13C
NMR (CDCl3, 100 MHz, ppm) δ 141.5, 140.3, 139.0, 137.5,
130.6, 129.8, 129.7, 129.5, 129.2, 127.5. ESI-MS [M+H]+ m/z
(E)-1-methyl-4-(styrylsulfonyl)benzene
(3f):[1]
Eluent
petroleum ether/ethyl acetate (10:1), pale yellow solid, mp 102–
o
1
103 C. H NMR (CDCl3, 400 MHz, ppm) δ 7.85 (d, 2H, J = 8.0 85 313.1.
Hz), 7.68 (d, 1H, J = 16 Hz), 7.51-7.49 (m, 2H), 7.42-7.36 (m,
1-chloro-3-(1-iodo-2-(methylsulfonyl)ethyl)benzene
(3n):
30 5H), 6.87 (d, 1H, J = 16 Hz), 2.46 (s, 3H). 13C NMR (CDCl3, 100
MHz, ppm) δ 144.4, 141.9, 137.8, 132.4, 131.1, 130.0, 129.1,
128.5, 127.7, 127.6, 21.6. ESI-MS [M+H]+ m/z 259.3.
Eluent petroleum ether/ethyl acetate (10:1), pale yellow solid, mp
1
= 85−87 °C. H NMR (CDCl3, 400 MHz, ppm) δ 7.52 (s, 1H),
7.42-7.39 (m, 1H), 7.33-7.31 (m, 2H), 5.53 (dd, 1H, J = 8 Hz),
(E)-1-methyl-2-(2-tosylvinyl)benzene (3g): Eluent petroleum 90 4.14-4.08 (dd, 1H, J1 = 8 Hz, J2 = 12 Hz), 3.95-3.90 (dd, 1H, J1 =
o
1
ether/ethyl acetate (10:1), white solid, mp 126–127 C. H NMR
35 (CDCl3, 400 MHz, ppm) δ 7.94 (d, 1H, J = 16 Hz),7.84 (d, 2H, J
= 8 Hz), 7.65 (d, 1H, J = 16 Hz), 7.34 (d, 2H, J = 8 Hz), 7.32-
7.29 (m, 3H), 6.85 (d, 1H, J = 16 Hz), 2.46 (s, 3H), 2.37 (s, 3H).
13C NMR (CDCl3, 100 MHz, ppm) δ144.4, 139.7, 138.2, 137.9,
131.5, 131.1, 130.9, 130.1, 128.7, 127.8, 126.9, 126.5, 21.7, 19.9.
40 ESI-MS [M+H]+ m/z 273.3.
8 Hz, J2 = 12 Hz), 2.51 (s, 3H). 13C NMR (CDCl3, 100 MHz,
ppm) δ 143.0, 135.1, 130.6, 129.4, 127.7, 125.6, 65.4, 42.6, 15.5.
ESI-MS [M+H]+ m/z 361.3.
(1-iodo-2-(methylsulfonyl)ethyl)benzene (3o): Eluent petroleum
95 ether/ethyl acetate (10:1). colorless oil. 1H NMR (CDCl3, 400
MHz, ppm) δ 7.53 (d, 1H, , J = 8 Hz), 7.41-7.34 (m, 3H), 5.58
(dd, 1H, J = 4 Hz), 4.17 (dd, 1H, J1 = 8 Hz, J2 = 12 Hz), 3.94 (dd,
1H, J1 = 8 Hz, J2 = 4 Hz), 2.35 (s, 3H). 13C NMR (CDCl3, 100
MHz, ppm) δ 140.9, 129.4, 127.5, 125.7, 65.7, 42.4, 17.5. ESI-
(E)-1-methyl-3-(2-tosylvinyl)benzene (3h): Eluent petroleum
o
1
ether/ethyl acetate (10:1), white solid, mp 82–83 C. H NMR
(CDCl3, 400 MHz, ppm) δ 7.93 (d, 1H, J = 16 Hz), 7.82 (d, 2H, J 100 MS [M+H]+ m/z 311.1.
= 8 Hz), 7.41 (d, 1H, J = 8 Hz), 7.33 (d, 2H, J = 8 Hz), 7.25-7.21
45 (m, 1H), 7.20 (t, 2H, J = 8 Hz), 6.76 (d, 1H, J = 16 Hz), 2.44 (s,
3H), 2.43 (s, 3H). 13C NMR (CDCl3, 100 MHz, ppm) δ144.3,
142.2, 138.8, 137.9, 132.4, 131.9, 129.9, 129.1, 128.9, 127.7,
127.4, 125.8, 21.6, 21.3. ESI-MS [M+H]+ m/z 273.3.
Conclusions
In conclusion, we have developed a highly efficient, green and
practical iodine-mediated method for the synthesis of vinyl
sulfones. The method enjoys the following advantages of: (a)
105 commercially available and non-toxic molecular iodine as the
catalyst; (b) environmentally friendly water as the solvent (c) no
addition of any base or additive; (d) all the reactions performed at
room temperature; (e) easy workup procedure; (f) outstanding
tolerance of functional groups. All these merits can meet the
110 requirements of green and sustainable chemistry. Therefore, the
developed synthesis method will attract much attention in
academic and industrial fields. Further investigation on the
applications of this method is in progress.
(E)-1-fluoro-4-(2-tosylvinyl)benzene (3i): Eluent petroleum
50 ether/ethyl acetate (10:1), yellow oil. 1H NMR (CDCl3, 400 MHz,
ppm) δ 7.84 (d, 2H, J = 8 Hz), 7.63 (d, 1H, J = 16 Hz), 7.50-7.47
(m, 2H), 7.36 (d, 2H, J = 8 Hz), 7.11-7.06 (m, 2H), 6.81 (d, 1H, J
= 16 Hz), 2.45 (s, 3H). 13C NMR (CDCl3, 100 MHz, ppm) δ
144.5, 140.7, 137.8, 130.7, 130.6, 130.1, 128.9, 127.8, 127.5,
55 116.5, 116.3, 21.7. ESI-MS [M+H]+ m/z 278.1.
(E)-1-chloro-4-(2-tosylvinyl)benzene (3j):[4] Eluent petroleum
ether/ethyl acetate (10:1), white solid, mp = 140−141 °C. 1H
4
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