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for approximately 24 h at 60 ꢁC (oil bath temperature). The
system was cooled to room temperature and saturated aqueous
NH4Cl solution (20 mL) was added; the mixture was extracted
with CH2Cl2 (2 ꢂ 20 mL), the organic layer was dried over
MgSO4, ltered and concentrated under reduced pressure. The
residue was puried by column chromatography, eluting with
ethyl acetate/hexanes (1 : 9, v/v).
Diethyl ((phenylsulnyl)methyl)phosphonate (4). This
compound was synthesized according to the literature.54 NaIO4
(1.302 g, 6.09 mmol) was dissolved in a 1 : 2 mixture of THF/
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H2O (15 mL) and cooled to 0 C. A solution of 1 (1.507 g, 5.79
mmol) in THF (5 mL) was added dropwise. The mixture was
stirred at room temperature for 93 h. The solvent was removed
under reduced pressure and the resulting crude mixture was
diluted with EtOAc, washed with saturated aqueous NH4Cl,
dried over MgSO4 and concentrated under vacuum. The crude
product was puried by ash chromatography (EtOAc/hexanes,
N,N-Diphenyl-4-(2-(phenylsulnyl)vinyl)aniline (P3). Yellow
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solid. Yield: 0.579 g (71%). Mp: 44 C. E/Z: 7/1. H NMR (400
MHz, CDCl3, TMS) E/Z isomers d (ppm): 7.69–7.65 (m, 2H),
7.52–7.44 (m, 3H), 7.15–6.96 (m, 8H), 6.67 (d, J ¼ 15.5 Hz, 1H, E),
6.29 (d, J ¼ 10.6 Hz, 1H, Z). 13C NMR (100 MHz, CDCl3, TMS)
d (ppm): 121.2, 124.0, 124.4, 125.0, 125.6, 127.5, 129.2, 129.6,
129.8, 133.0, 141.5, 142.3, 146.7, 150.8. FTIR (n/cmꢀ1): 3448,
3032, 1589, 1489, 1327, 1280, 1080, 1033, 748, 694. (ESI-MS) m/z:
[M + H]+ calcd for C26H21NOS 396.1417, found 396.1445.
(E)-1-(2-(Phenylsulnyl)vinyl)pyrene (P4). Yellow solid. Yield:
0.540 g (68%). Mp: 183 ꢁC. 1H NMR (400 MHz, CDCl3, TMS)
d (ppm): 8.42 (d, J ¼ 15.1 Hz, 1H), 8.39 (d, 1H), 8.16–7.93 (m,
8H), 7.77 (d, 2H), 7.55–7.47 (m, 3H), 7.04 (d, J ¼ 15.2 Hz, 1H).
13C NMR (100 MHz, CDCl3, TMS) d (ppm): 122.4, 124.3, 124.6,
124.9, 125.7, 125.9, 126.3, 127.2, 127.5, 128.4, 128.6, 129.2,
129.6, 130.7, 131.2, 131.3, 132.3, 133.4, 135.1, 144.1. FTIR (n/
cmꢀ1): 3441, 3047, 1597, 1087, 1049, 941, 848, 709. Anal. calcd
for C24H16OS: C, 81.79; H, 4.58. Found: C, 80.99; H, 5.08.
General procedure for the preparation of vinyl sulfones. To
a dry 50 mL two-necked ask were added the vinyl sulde P1 or
P2 (0.5 mmol) and CH2Cl2 (15 mL). The system was cooled with
ice-water bath and mCPBA (50%, 0.516 g, 1.5 mmol) was added
and the reaction was stirred for approximately 24 h at room
temperature. The reaction mixture was diluted with CH2Cl2 (10
mL) and washed with 30% Na2S2O3 solution (2 ꢂ 15 mL) and
5% NaHCO3 solution (3 ꢂ 15 mL). The organic layer was dried
over MgSO4 and concentrated under reduced pressure. The
residue was puried by column chromatography, eluting with
ethyl acetate/hexanes (2 : 8, v/v).
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7 : 3, v/v) to yield 4 (1.03 g, 65%) as a light yellow oil. H NMR
(200 MHz, CDCl3) d (ppm): 7.77–7.65 (m, 2H), 7.60–7.51 (m, 3H),
4.25–4.03 (m, 4H), 3.50–3.22 (m, 2H), 1.36–1.21 (m, 6H).
General procedure for the preparation of the vinyl suldes.
Under an argon atmosphere, a dry 50 mL two-necked ask was
charged with diethyl phenylthiomethylphosphonate (1, 0.911 g,
3.5 mmol) and THF (30 mL) at room temperature. NaH (60% in
mineral oil; 0.139 g, 3.5 mmol) was added to the solution and
stirred for 15 min. Aer this time, the appropriate carbonyl
compound (3 mmol) was added and the reaction was stirred for
approximately 24 h at 60 ꢁC (oil bath temperature). The system
was cooled to room temperature, a saturated aqueous NH4Cl
solution (20 mL) was added, the mixture was extracted with
CH2Cl2 (2 ꢂ 20 mL), and the organic layer was dried over
MgSO4, ltered and concentrated under reduced pressure. The
residue was puried by column chromatography, eluting with
ethyl acetate/hexanes (1 : 9, v/v).
N,N-Diphenyl-4-(2-(phenylthio)vinyl)aniline (P1). Pale yellow
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solid. Yield: 1.058 g (93%). Mp: 126 C. E/Z: 6/1. H NMR (400
MHz, CDCl3, TMS) E/Z isomers d (ppm): 7.52–7.43 (m, 2H),
7.40–7.25 (m, 9H), 7.18–7.04 (m, 8H), 6.81 (d, J ¼ 15.4 Hz, 1H, E),
6.76 (d, J ¼ 15.4 Hz, 1H, E), 6.58 (d, J ¼ 10.7 Hz, 1H, Z), 6.44 (d, J
¼ 10.7 Hz, 1H, Z). 13C NMR (100 MHz, CDCl3, TMS) d (ppm):
120.9, 123.1, 123.2, 123.5, 124.6, 124.6, 126.7, 127.0, 129.1,
129.3, 129.5, 129.8, 129.9, 130.7, 132.5, 135.9, 147.6. FTIR (n/
cmꢀ1): 3417, 3016, 1589, 1489, 1327, 1280, 1072, 740, 686, 640.
Anal. calcd for C26H21NS: C, 82.28; H, 5.58; N, 3.69. Found: C,
82.18; H, 5.35; N, 3.24.
(E)-N,N-Diphenyl-4-(2-(phenylsulfonyl)vinyl)aniline
(P5).
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Yellow solid. Yield: 0.160 g (78%). Mp: 161 ꢁC. H NMR (400
MHz, CDCl3, TMS) d (ppm): 7.93–7.90 (m, 2H), 7.61–7.49 (m,
4H), 7.31–7.24 (m, 6H), 7.10–7.07 (m, 6H), 6.96 (d, J ¼ 8.7 Hz,
2H), 6.66 (d, J ¼ 15.3 Hz, 1H). 13C NMR (100 MHz, CDCl3, TMS)
d (ppm): 121.2, 124.0, 124.4, 125.0, 125.6, 127.5, 129.2, 129.6,
129.8, 133.0, 141.5, 142.3, 146.7, 150.8. FTIR (n/cmꢀ1): 3448,
3047, 1581, 1489, 1334, 1303, 1141, 1080, 702, 617, 501. (ESI-
MS) m/z: [M + H]+ calcd for C26H21NO2S 412.1366, found
412.1385.
Phenyl(2-(pyren-1-yl)vinyl)sulfane (P2). Pale yellow solid.
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Yield: 0.898 g (89%). Mp: 112 C. E/Z: 5/1. H NMR (400 MHz,
CDCl3, TMS) E/Z isomers d (ppm): 8.23–8.19 (m, 1H), 8.13–7.89
(m, 7H), 7.70 (d, J ¼ 15.2 Hz, 1H, E), 7.51–7.40 (m, 2H), 7.36–7.18
(m, 3H), 7.07 (d, J ¼ 15.2 Hz, 1H, E), 6.81 (d, J ¼ 10.4 Hz, 1H, Z).
13C NMR (100 MHz, CDCl3, TMS) d (ppm): 122.9, 123.6, 124.5,
124.9, 125.0, 125.1, 125.3, 126.0, 126.6, 127.2, 127.3, 127.4,
127.7, 127.8, 128.7, 129.2, 129.3, 130.0, 130.1, 130.9, 130.9,
131.1, 131.6, 135.3. FTIR (n/cmꢀ1): 3471, 3425, 3016, 1573, 1473,
1087, 941, 840, 740, 694. Anal. calcd for C24H16S: C, 85.68; H,
4.79. Found: C, 85.28; H, 4.57.
(E)-1-(2-(Phenylsulfonyl)vinyl)pyrene (P6). Yellow solid.
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Yield: 0.138 g (75%). Mp: 190 C. H NMR (400 MHz, CDCl3,
TMS) d (ppm): 8.75 (d, J ¼ 15.1 Hz, 1H), 8.36 (d, 1H), 8.20–
7.96 (m, 10H), 7.64–7.52 (m, 3H), 7.08 (d, J ¼ 15.1 Hz, 1H).
13C NMR (100 MHz, CDCl3, TMS) d (ppm): 121.9, 124.4,
124.8, 124.9, 125.7, 126.2, 126.3, 126.4, 127.2, 127.8, 128.7,
129.1, 129.4, 130.1, 130.5, 131.2, 133.3, 133.4, 139.2, 141.0.
FTIR (n/cmꢀ1): 3417, 2916, 1597, 1319, 1149, 1080, 840, 578.
(ESI-MS) m/z: [M + H]+ calcd for C24H16O2S 369.0944, found
369.0960.
General procedure for the preparation of the vinyl sulfox-
ides. To a dry 50 mL two-necked ask, under argon atmosphere,
was added diethyl ((phenylsulnyl)methyl)phosphonate (4,
0.54 g, 1.95 mmol) and THF (15 mL) at room temperature. NaH
(60% in mineral oil; 0.078 g, 1.95 mmol) was added to solution
and stirred for 15 min. Aer this time, the appropriate carbonyl
compound (1.67 mmol) was added and the reaction was stirred
8834 | RSC Adv., 2017, 7, 8832–8842
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