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Y. Guo, Q.-Y. Chen / Journal of Fluorine Chemistry 107 (2001) 89±96
was poured into water and extracted three times with ether
(3 Â 10 ml). The combined extracts were washed with water
(3 Â 5 ml) and dried over Na2SO4. After the ether had been
evaporated, the residue was subjected to chromatography on
silica gel to give 4c (0.05 g, 10%).
(11.65), 77 (14.24). Analysis: calc. for C20H28F2O4: C,
64.84%; H, 7.61%; F, 10.26%. Found: C, 64.68%; H,
7.57%; F, 10.30%.
3.3. General procedure for the reactions of 1 or 12b with 6
4c: Colorless oil. IR (®lm) (cm 1): 2900, 1800, 1740,
1
1640, 1200, 1100. H NMR (CDCl3, 300 MHz) d (ppm):
Compound 1b (1.00 g, 2 mmol) was added to 6b (0.69 g
p-chlorothiophenol reacted with equimolar amount of NaH
in DMF (10 ml). After the reaction was complete, the
mixture was poured into water, to which HCl (10 ml, 1N)
was added. The aqueous layer was extracted three times with
ether (3 Â 20 ml). The combined extracts were washed with
water (3 Â 10 ml) and dried over Na2SO4. After the ether
had been evaporated, the residue was subjected to chroma-
tographyonsilicageltogive7bband8bb(0.63 g, yield81%).
A pure sample of 8aa, 8ba, 8ca, 8da or 8db was not
isolated from 7, but identi®ed by 19F NMR.
1.20±1.73 (m, 15H), 2.28 (t, J 7:5 Hz, 2H), 2.31 (d,
J 6:4 Hz, 2H), 4.12 (q, J 7:1 Hz, 2H), 5.80 (dtt,
J 15:6, 8.2, 1.4 Hz, 1H), 7.18 (dt, J 14:6, 7 Hz, 1H).
19F NMR (CDCl3, 282 MHz) d (ppm):
102.2 (d,
J 7:7 Hz). MS m/z (relative intensity): 239 (1.33), 213
(32.19), 164 (21.86), 55 (100.00).
3.2. General procedure for the reactions of 1 with 11
Compound 1c (1.02 g, 2 mmol) was added to 11a (0.42 g
phenol reacted with equimolar amount of NaH) in DMF
(10 ml) at room temperature. After 4 h, the mixture was
poured into water, to which HCl (10 ml, 1N) was added. The
aqueous layer was extracted three times with ether
(3 Â 20 ml). The combined extracts were washed with water
(3 Â 10 ml) and dried over Na2SO4. After the ether had been
evaporated, the residue was subjected to chromatography on
silica gel to give 5ca (0.57 g, yield 80%).
7aa: Isolated from PhSSPh by distillation. Colorless oil,
b.p. 738C/mmHg. IR (®lm) (cm 1): 2900, 1740, 1580, 1440,
1
1280, 1170. H NMR (CDCl3, 300 MHz) d (ppm): 0.91 (t,
J 7:2 Hz, 3H), 1.30±1.78 (m, 6H), 3.84 (m, 1H), 4.18
(ddd, J 24:0, 10.8, 2.0 Hz), 7.26±7.45 (m, 5H). 19F NMR
(CDCl3, 282 MHz) d (ppm): 10.8 (d, J 41:8), 12.2 (dd,
J 41:7, 24.0 Hz). MS m/z (relative intensity): 242 (M ,
12.64%), 133 (16.41), 110 (75.16), 109 (33.68), 77 (100.00).
HRMS: calc. for C13H16F2S: 242.0941. Found: 242.0968.
7ba: Colorless oil. IR (®lm) (cm 1): 2900, 1740, 1580,
5ca: Colorless oil. IR (®lm) (cm 1): 2930, 1730, 1590,
1
1490, 1120. H NMR (CD3COCD3, 300 MHz) d (ppm):
1
1.18±1.59 (m, 15H), 2.14 (d, J 2:4 Hz, 2H), 2.19 (t,
J 7:4 Hz, 2H), 4.08 (q, J 7:1 Hz, 2H), 5.81 (dtt,
J 15:5, 6.9, 1.5 Hz, 1H), 6.42 (dtt, J 15:6, 6.9,
2.2 Hz, 1H), 7.20±7.44 (m, 5H). 19F NMR (CDCl3,
282 MHz) d (ppm): 16.1 (s). MS m/z (relative intensity):
335 (8.56), 309 (25.83), 261 (44.39), 175 (32.03), 133
(52.37), 94 (100.00). Analysis: calc. for C20H28F2O3: C,
67.77%; H, 7.96%; F, 10.72%. Found: C, 67.13%; H, 8.13%;
F, 10.76%.
1440, 1170. H NMR (CDCl3, 300 MHz) d (ppm): 1.36±
1.77 (m, 14H), 2.30 (t, J 7:5 Hz, 2H), 3.65 (s, 3H), 3.80
(m, 1H), 4.16 (ddd, J 24:1, 10.6, 2.0 Hz, 1H), 7.23±7.43
(m, 5H), 19F NMR (CDCl3, 282 MHz) d (ppm): 10.2 (d,
J 41:7 Hz), 11.4 (dd, J 41:6, 24.0 Hz). MS m/z (rela-
tive intensity): 356 (M , 2.50%), 247 (100.00), 175 (58.25),
110 (71.79). Analysis: calc. for C19H26F2O2S: C, 64.01%; H,
7.35%; F, 10.66%. Found: C, 64.25%; H, 7.34%; F, 10.54%.
HRMS: calc. for C19H26F2O2S: 356.1622. Found: 356.1641.
7bb: Colorless oil. IR (®lm) (cm 1): 2931, 2857, 1738,
1574, 1477, 1178, 1096, 1014, 823. 1H NMR (CDCl3,
5ba: Colorless oil. IR (®lm) (cm 1): 2926, 1736, 1676,
1626, 1590, 1491, 1437, 1320, 1200, 1182, 1123, 1035, 975,
756, 694. 1H NMR (CD3COCD3, 300 MHz) d (ppm): 1.43±
1.61 (m, 12H), 2.17 (m, 2H), 2.27 (m, 2H), 3.61 (s, 3H), 5.81
(dtt, J 15:5, 7.0, 1.5 Hz, 1H), 6.41 (dtt, J 15:7, 7.0,
2.0 Hz, 1H), 7.21±7.44 (m, 5H). 19F NMR (CD3COCD3,
282 MHz) d (ppm): 16.1 (d, J 5:4 Hz). MS m/z (relative
intensity): 321 (100.00), 309 (7.75), 247 (13.05), 207 (6.10),
175 (9.10), 133 (10.51), 94 (9.60). Analysis: calc. for
C19H26F2O3: C, 67.04%; H, 7.70%; F, 11.16%. Found: C,
66.81%; H, 7.51%; F, 11.04%.
300 MHz)
d (ppm): 0.96±1.23 (m, 14H), 2.31 (t,
J 7:5 Hz, 2H), 3.67 (s, 3H), 3.78 (m, 1H), 4.15 (ddd,
J 24:0, 10.8, 1.9 Hz, 1H), 7.29 (m, 4H). 19F NMR
(CDCl3, 282 MHz) d (ppm): 10.3 (d, J 40:9 Hz), 11.8
(dd, J 41:2, 24.0 Hz). MS m/z (relative intensity): 390
(M , 0.51%), 389 (1.79), 247 (79.81), 175 (54.29), 133
(74.74), 55 (100.00). Analysis: calc. for C19H25ClF2O2S: C,
58.37%; H, 6.45%; F, 9.72%. Found: C, 58.31%; H, 6.44%;
F, 9.74%.
5bb: Colorless oil. IR (®lm) (cm 1): 2923, 1735, 1676,
1600, 1499, 1458, 1438, 1265, 1202, 1173, 1117, 1032, 975,
7bc: Colorless oil. IR (®lm) (cm 1): 2900, 1740, 1280,
1170. 1H NMR (CDCl3, 300 MHz) d (ppm): 1.28±1.72 (m,
17H), 2.32 (t, J 7:6 Hz, 2H), 3.23 (dd, J 20:7, 15.2 Hz,
2H), 3.70 (m, 4H),4.20 (m, 3H). 19F NMR (CDCl3,
282 MHz) d (ppm): 9.73 (d, J 41:5 Hz), 12.0 (dd,
1
882, 783, 754. H NMR (CD3COCD3, 300 MHz) d (ppm):
1.24±1.59 (m, 12H), 2.13 (m, 2H), 2.25 (m, 2H), 3.60 (s,
3H), 3.82 (s, 3H), 5.75 (dtt, J 15:6, 7.2, 1.4 Hz, 1H), 6.35
(dtt, J 15:5, 7.0, 2.1 Hz, 1H), 6.89±7.34 (m, 4H). 19F
J 41:6, 24.1 Hz). MS m/z (relative intensity): 366 (M ,
NMR (CD3COCD3, 282 MHz) d (ppm):
16.2 (d,
1.16%), 346 (1.53), 279 (49.15), 247 (100.00), 175 (38.03).
Analysis: calc. for C17H28F2O4S: C, 55.71%; H, 7.70%; F,
10.37%. Found: C, 55.92%; H, 7.81%; F, 10.31%.
J 5:1 Hz). MS m/z (relative intensity): 370 (M ,
6.84%), 351 (40.40), 339 (6.64), 124 (100.00), 109