1
08
Y. Guo, Q.-Y. Chen / Journal of Fluorine Chemistry 102 (2000) 105±109
�
1
h: Colorless oil. IR (®lm) (cm ): 3394, 2280, 1578,
1
4
472, 1444, 1227, 1174, 1118, 1051, 1033, 1004, 865, 759,
1058, 838, 806, 750, 706, 683, 639, 610. H NMR (CCl ) d
4
19
1
7
(ppm): 7.1±7.7 (m). F NMR (CCl ) d (ppm): � 61.0. MS
4
1
19
04, 655. H NMR (CCl ) d (ppm): 6.90±7.90 (4H, m).
F
m/z (relative intensity): 319 (0.40), 196 (2.90), 195 (34.55),
194 (9.46), 193 (100), 143 (11.23), 111 (18.14). Analysis:
calc.for C H ClF IS: C, 26.20%; H, 1.24%; found: C,
4
NMR (CCl ) d (ppm): � 74.6. MS m/z (relative intensity):
4
3
(
1
49 (6.02), 348 (70.54), 346 (70.80), 283 (4.63), 282
66.21), 280 (67.91), 177 (6.33), 157 (4.02), 156 (46.61),
54 (47.39), 127 (12.28), 75 (100). HRMS: calc. for
7
4
2
25.65%; H, 1.06%.
�
1
8b: White needle. m.p. 136±1388C. IR (®lm) (cm ):
3083, 1907, 1715, 1635, 1570, 1474, 1452, 1390, 1270,
1095, 1084, 1048, 1026, 1017, 970, 956, 898, 877, 827, 753,
7
9
C H Br F IO: 347.8457; found: 347.8474. calc. for
7
8
C H Br F IO: 349.8437; found: 349.8477.
4
2
1
7
4
2
�
1
1
19
3
h: White solid. m.p. 74±768C. IR (KBr) (cm ): 1783,
711, 660. H NMR (CCl ) d (ppm): 7.3±7.7 (m). F NMR
4
1
472, 1445, 1238, 1197, 1159, 1045, 1028, 1006, 760, 740.
(CCl ) d (ppm): � 28.0. MS m/z (relative intensity): 337
4
1
H NMR (CCl ) d (ppm): 6.7±8.2 (m). MS m/z (relative
intensity): 374 (6.51), 372 (12.73), 370 (6.48), 293 (35.19),
2
1
(9.17), 335 (12.74), 195 (77.22), 193 (100), 143 (25.61), 111
(37.69). Analysis: calc. for C H Cl F I S : C, 49.29%; H,
2.37%; found: C, 49.24%; H, 2.17%.
4
13
8
2 2 2 2
91 (35.20), 201 (8.26), 199 (8.44), 168 (100), 157 (30.95),
55 (32.29), 75 (28.74), 63 (39.62). Analysis: calc. for
�
1
9b: colorless oil. b.p. 46±52/1 mm Hg. IR(®lm) (cm ):
2970, 1898, 1643, 1573, 1476, 1443, 1391, 1320, 1298,
C H Br O : C, 41.97%; H, 2.17%; found: C, 41.90%;
1
3
8
2 3
1
1071, 1043, 1018, 830, 792, 765, 743, 705, 683, 604. H
H, 2.10%.
i: Colorless oil. IR (®lm) (cm ): 3008, 2942, 2840,
1
1
�
1
4
604, 1502, 1465, 1441, 1384, 1308, 1285, 1266, 1176,
NMR (CDCl ) d (ppm): 7.41 (4H, m), 7.00±6.62 (1H, t,
3
19
JHF 56.6 Hz). F NMR (CDCl ) d (ppm): 13.83 (d,
3
1
120, 1047, 1029, 996, 866, 784, 754, 690. H NMR (CCl )
JFH 56.6 Hz). MS m/z (relative intensity): 196 (40.52),
195 (17.50), 194 (100), 146 (37.85), 145 (29.87), 144
(97.54), 143 (56.47), 108 (55.35).
4
19
d (ppm): 6.70±7.50 (4H, m), 3.84 (3H, s). F NMR (CCl ) d
4
(
(
(
ppm): � 76.1. MS m/z (relative intensity): 300 (0.50), 299
4.34), 174 (11.30), 173 (100), 92 (37.57), 79 (44.09), 77
68.01), 63 (14.51). HRMS: calc. for C H F IO : 299.9457;
3.3. The preparation of 8b from 7b and the inhibition of
the experiment
8
7
2
2
found: 299.9450.
�
1
3
i: White needle. m.p. 88±898C. IR (KBr) (cm ): 1783,
1
472, 1445, 1238, 1197, 1159, 1045, 1028, 1006, 760, 740.
The thiophenol 5b (0.07 g, 0.5 mmol), NaH (75% in oil,
0.02 mg, 0.5 mmol) were reacted in DMF (5 ml) under
nitrogen for an hour. To this solution, 7b (0.15 g, 0.5 mmol)
was added. The mixture was stirred at room temperature for
an hour. After work-up as usual, 8b (0.11 g, 65%) was
obtained.
1
H NMR (CCl ) d (ppm): 6.7±8.2 (m), 4.00 (3H, s). MS m/z
4
(
(
(
relative intensity): 374 (6.51), 372 (12.73), 370 (6.48), 293
35.19), 291 (35.20), 201 (8.26), 199 (8.44), 168 (100), 157
30.95), 155 (32.29), 75 (28.74), 63 (39.62). Analysis: calc.
for C H O : C, 65.75%; H, 5.15%; found: C, 65.76%; H,
1
5 14 5
5
.11%.
A parallel experiment, i.e., with and without p-PNB
20 mmol%), of the same procedure(0.5 mmol of 7b and
(
0.5 mmol of p-ClC H S in DMF) were run under nitrogen
�
3.2. General procedure for the reactions of 1 with sodium
thiophenoxides
6
4
at room temperature. After 10 min, the conversion of 7b was
0% determined by the decrease of signal ICF SC H Cl-p
6
2
6 4
19
To a 25 ml three-necked round bottomed ¯ask, equipped
with stirrer, 5a (0.54, 4.9 mmol), NaH (75% in oil, 0.16 g,
(� 61.0 ppm) in F NMR spectroscopy while that was only
30% in the presence of p-PNB. Both reactions did not
continue if the experiments were exposed to air at this
moment.
5
(
5
mmol), and DG (5 ml) were added under nitrogen. 1
1.50 g, 5 mmol) was dropped into the ¯ask slowly. After
h, the mixture was poured into water. The aqueous
layer was extracted three times with ether (3 Â 20 ml).
3.4. The attempt to prepare 10c from 4c
The combined extracts were washed with water
(
3 Â 10 ml) and dried over Na SO . After the ether had
The phenol 2c (0.28 g, 3 mmol) and NaH (75% in oil,
0.09 g, 3 mmol) were reacted in DMF (5 ml) under nitrogen
for an hour. Then, 4c (0.27 g, 1 mmol) was added and the
mixture was stirred at room temperature for 5 h. After work-
up as usual, 4c was recovered 0.15 g (55%) and none of 3c
was detected.
2
4
been evaporated, the residue was subjected to chromato-
graphy on silica gel to give thiophenyl di¯uoroiodomethyl
ether as an oil, 7a (0.18 g, 13%), and diphenyldisul®de 6a
(
0.28 g, 54%).
1
7
a: Colorless oil. H NMR (CCl ) d (ppm): 7.1±7.8 (m).
4
1
9
F NMR (CCl ) d (ppm): � 63.0. MS m/z (relative inten-
4
sity): 286 (M , 0.26), 177 (CF I , 0.74), 159 (M � I, 100),
2
1
2
09 (12.29), 77 (47.74). Analysis: calc. for C H F IS: C,
7
Acknowledgements
5 2
9.37%; H, 1.74%; found: C, 29.11; H, 1.61.
b: Colorless oil. b.p. 70±768C/1 mm Hg. IR (®lm)
cm ): 2109, 1897, 1801, 1571, 1474, 1461, 1390, 1301,
7
We thank the Chinese National Natural Science Founda-
tion for the ®nancial support.
�
1
(