248 Letters in Organic Chemistry, 2009, Vol. 6, No. 3
Ying et al.
equivalents of the appropriate Grignard reagent. The reaction
was heated to reflux for 18 hours. The solution was cooled to
room temperature, then to –78°C and sulfur dioxide gas was
condensed into the flask over 5 minutes. The brown solution
turned to a yellow color as the solution warmed to 25°C over
the next hour. The reaction was quenched by stirring the
solution with aqueous ammonium chloride (30 mL of a satu-
rated solution) and performing an aqueous ether extraction (3
X 50 mL ether). The extracted ether was washed with water
and brine. The ethereal solution was dried using magnesium
sulfate and the solvent removed by rotary evaporation. The
residue was dissolved in a small amount of chloroform and
treated with pentane until a precipitate formed. The precipi-
tate was filtered and the solution was condensed to an oil
using rotary evaporation. The product was obtained follow-
ing chromatography on SiO2 and removal of the solvent by
rotary evaporation and high vacuum.
Hz, 1H), 5.86 (d, J=14.5 Hz, 1H), 6.37 (dd, J=11.0 Hz,
J=17.8 Hz, 1H), 6.97 (m, 2H), 7.48 (m, 1H). 13C NMR (75.4
MHz, CDCl3): 81.57, 105.24 (t, J=25.6 Hz), 112.58 (d, J=4.1
Hz), 112.65 (dd, J=3.8 Hz, J=21.7 Hz), 124.13, 126.91,
132.92 (dd, J=4.0 Hz, J=9.9 Hz), 140.05 (d, J=1.9 Hz),
142.23, 160.76 (dd, J=12.1 Hz, J=252.8 Hz), 164.36 (dd,
J=11.5 Hz, J=253.0 Hz).
3-(2, 4-Difluorophenyl)-4-phenyl-(1,2)-oxathiol-3-en-2-
oxide (23)
3-(2, 4-Difluorophenyl)-2-propyn-1-ol (16) (100 mg,
0.595 mmol) and phenylmagnesium bromide (5.95 mL of a
1.0 M solution, 5.95 mmol) were allowed to react as de-
scribed above. The reaction was performed using the proce-
dure described above. The reaction yielded 3-(2, 4-Difluoro-
phenyl)-4-phenyl-(1,2)-oxathiol-3-en-2-oxide (0.093g, 0.318
mmol, 54%) as a white solid. Anal. Calcd for C15H10F2SO2:
1
C, 61.64; H, 3.45. Found: C, 61.53; H, 3.57. H NMR (300
3-(2’,3’-Dichlorophenyl)-4-vinyl-(1,2)-oxathiol-3-en-2-
oxide (20)
MHz, CDCl3): 5.57 (d, J=15.1 Hz, 1H), 5.94 (d, J=15.1 Hz,
1H), 6.83 (m, 2H), 7.12 (m, 2H), 7.21 (m, 2H), 7.28 (m, 1H),
7.38 (m, 1H). 13C NMR (75.4 MHz, CDCl3): 83.35, 104.84 (t,
J=25.4 Hz), 112.31 (dd, J=3.9 Hz, J=21.4 Hz), 113.01 (dd,
J=4.2 Hz, J=15.8 Hz), 127.51, 128.97, 129.62, 130.12,
132.34 (dd, J=4.1 Hz, J=9.8 Hz), 137.28 (d, J=2.2 Hz),
144.22, 160.25 (dd, J=12.4 Hz, J=253.5 Hz), 163.73 (dd,
J=12.0 Hz, J=253.1 Hz).
3-(2,3-Dichlorophenyl)-prop-2-yn-1-ol (13) (0.100 g,
0.50 mmol) and vinyl magnesium bromide (5 mL of 1.0 M
soln, 5.00 mmol) were allowed to react as described above.
The pure product was obtained following chromatography
on SiO2 (1:3 ethyl acetate/hexane). The reaction produced a
yellow oily solid (0.070 g, 0.25 mmol, 51%). Anal. Calc’d
for C11H8Cl2O2S: C, 48.02; H, 2.93. Found: C, 48.00; H,
3.32. 1H NMR (300 MHz, CDCl3 ꢀ): 5.54 (m, 3H), 5.87 (d, J
= 14.4 Hz, 1H), 6.27 (dd, J = 18.6 Hz, J = 11.0 Hz, 1H), 7.30
(m, 2H), 7.56 (m, 1H). 13C NMR (300 MHz, CDCl3 ꢀ):
81.23, 124.21, 126.80, 128.20, 129.77, 131.16, 132.18,
133.09, 134.40, 142.15, 145.04.
3-(2, 4-Difluorophenyl)-4-(4-fluorophenyl)-(1,2)-oxathiol-
3-en-2-oxide (24)
3-(2, 4-Difluorophenyl)-2-propyn-1-ol (16) (100 mg,
0.595 mmol) was treated with 4-fluorophenylmagnesium
bromide (5.95 mL of a 1.0 M solution, 5.95 mmol). The re-
action was performed using the procedure described above.
The reaction yielded 3-(2, 4-Difluorophenyl)-4-(4-fluoro-
phenyl)-(1,2)-oxathiol-3-en-2-oxide (0.039g, 0.126mmol,
21%) as a white solid. 1H NMR (300 MHz, CDCl3): 5.63 (d,
J=15.1 Hz, 1H), 5.98 (d, J=15.1 Hz, 1H), 6.95 (m, 4H), 7.19
(m, 2H), 7.47 (m, 1H). 13C NMR (75.4 MHz, CDCl3): 83.71,
105.46 (t, J=25.4 Hz), 112.96 (dd, J=4.0 Hz, J=21.5 Hz),
113.29 (dd, J=4.0 Hz, J=15.6 Hz), 116.78 (d, J=21.9 Hz),
126.23 (d, J=3.4 Hz), 130.04 (d, J=8.5 Hz), 132.69 (dd,
J=3.9 Hz, J=9.8 Hz), 137.79, 143.55, 160.67 (dd, J=12.7 Hz,
J=253.8 Hz), 163.94 (d, J=252.1 Hz), 164.32 (dd, J=11.9 Hz,
J=253.4 Hz). HRMS Calcd for [C15H9F3O2S+H+]: 311.0354.
Found: 311.0354.
3-(3’-chloro-2’-fluorophenyl)-4-vinyl-(1,2)-oxathiol-3-en-
2-oxide (21)
3-(3-Chloro-2-fluorophenyl)-prop-2-yn-1-ol (14) (0.100
g, 0.54 mmol) and vinyl magnesium chloride (5 mL of a
1.6M soln, 8.00 mmol) were allowed to react as described
above. The pure product was obtained following chromatog-
raphy on SiO2 (1:3 ethyl acetate/hexane). The reaction pro-
duced a yellow oily solid (0.046 g, 0.18 mmol, 32%). Anal.
Calc’d for C11H8ClFO2S: C, 51.07; H, 3.12. Found: C, 51.31;
1
H, 3.75. H NMR (300 MHz, CDCl3 ꢀ): 5.49 (m, 3H), 5.82
(d, J = 14.5 Hz, 1H), 6.32 (dd, J = 17.9 Hz, J = 11.0 Hz, 1H),
7.11 (t, J = 8.0 Hz, 1 H), 7.33 (t, J = 6.9 Hz, 1 H), 7.43 (t, J =
7.5 Hz, 1H). 13C NMR (300 MHz, CDCl3 ꢀ): 81.61, 118.21
(d, J = 15.8 Hz), 122.61 (d, 17.9 Hz), 124.48, 125.51 (d, J =
4.8 Hz), 126.88 (d, J = 1.6 Hz), 130.12 (d, J = 1.7 Hz),
132.61, 140.06 (d, J = 2.0 Hz), 142.74, 155.93 (d, J = 252.3
Hz).
3-(2, 4-Difluorophenyl)-4-(4-methoxyphenyl)-(1,2)-oxa-
thiol-3-en-2-oxide (25)
3-(2, 4-Difluorophenyl)-2-propyn-1-ol (16) (100 mg,
0.595 mmol) was treated with 4-methoxyphenylmagnesium
bromide (5.95 mL of a 1.0 M solution, 5.95 mmol). The re-
action was performed using the procedure described above.
The reaction yielded 3-(2, 4-Difluorophenyl)-4-(4-methoxy-
phenyl)-(1,2)-oxathiol-3-en-2-oxide (0.048g, 0.149 mmol,
25%) as a white solid. Anal. Calcd for C16H12F2SO3: C,
3-(2, 4-Difluorophenyl)-4-vinyl-(1,2)-oxathiol-3-en-2-oxide
(22)
3-(2, 4-Difluorophenyl)-2-propyn-1-ol (16) (100 mg,
0.595 mmol) in THF (25mL) was treated with vinylmagne-
sium bromide (5.95 mL of a 1.0 M solution, 5.95 mmol).
The reaction was performed using the procedure described
above. The reaction yielded 3-(2, 4-Difluorophenyl)-4-vinyl-
(1,2)-oxathiol-3-en-2-oxide (0.042g, 0.173mmol, 29%) as a
white solid. Anal. Calcd for C11H8F2SO2: C, 54.54; H, 3.33.
Found: C, 54.99; H, 3.60. 1H NMR (300 MHz, CDCl3): 5.48
(d, J=14.5 Hz, 1H), 5.50 (d, J=17.8 Hz, 1H), 5.59 (d, J=11.0
1
59.62; H, 3.75. Found: C, 59.86; H, 3.90. H NMR (300
MHz, CDCl3): 3.79 (s, 3H), 5.63 (d, J=14.9 Hz, 1H), 5.98 (d,
J=14.9 Hz, 1H), 6.81 (m, 2H), 6.91 (m, 2H), 7.13 (m, 2H),
7.47 (m, 1H). 13C NMR (75.4 MHz, CDCl3): 55.26, 83.11,
104.89 (t, J=25.5 Hz), 112.35 (dd, J=3.8 Hz, J=21.5 Hz),
113.40 (dd, J=4.0 Hz, J=16.0 Hz), 114.44, 121.75, 129.09,
132.40 (dd, J=4.0 Hz, J=9.8 Hz), 135.23 (d, J=2.0 Hz),