Xu and Chen
(g) Com p ou n d 6ea . Pale yellow liquid. IR (film; cm-1):
2959, 2936, 1786, 1729, 1633, 1459, 1438, 1309, 1270, 1197,
1174, 1022. 1H NMR (CDCl3): δ 0.93 (t, J ) 7.2 Hz, 3H), 1.34-
1.43 (m, 4H), 1.76 (t, J ) 7.1 Hz, 2H), 2.74 (t, J ) 7.3 Hz, 2H),
3.84 (s, 3H), 6.67 (d, J ) 8.8 Hz, 1H), 7.19 (d, J ) 15.9 Hz,
1H)). 19F NMR (CDCl3): δ -110.30 (s, 2F). MS m/z (rel
intens): 211 (17.47), 198 (7.53), 171 (26.61), 159 (100.00), 41
(97.31). Anal. Calcd for C12H16F2O2: C, 62.60; H, 7.00; F, 16.50.
Found: C, 62.43; H, 7.15; F, 16.92.
(o) Com p ou n d 6jc. Pale brown solid. IR (film; cm-1): 3109,
3047, 1763, 1690, 1602, 1521, 1347, 1301, 1258, 1174, 1031.
1H NMR (CDCl3): δ 2.45 (s, 3H), 6.84 (d, J ) 16.2 Hz, 1H),
7.31 (dt, J ) 17.6 Hz, 2.7 Hz, 1H), 7.84-7.87 (m, 2H), 8.36-
8.39 (m, 2H). 19F NMR (CDCl3): δ -113.17 (s, 2F). MS m/z
(rel intens): 265 (M+, 32.86), 250 (2.93), 222 (22.02), 176
(39.43), 43 (100.00). Anal. Calcd for C13H9F2NO3: C, 58.87; H,
3.42; N, 5.28; F, 14.33. Found: C, 58.35; H, 3.65; N, 5.04; F,
14.37.
(h ) Com p ou n d 6eb. Pale yellow liquid. IR (film; cm-1):
2961, 2935, 2865, 1782, 1721, 1695, 1468, 1421, 1318, 1280,
1222, 1118, 1023. 1H NMR (CDCl3): δ 0.90-0.95 (m, 3H),
1.36-1.41 (m, 4H), 1.68-1.72 (m, 2H), 2.59-2.65 (m, 2H), 6.57
(t, 1H), 7.03-7.09 (d d, 1H), 9.72 (d, 1H)). 19F NMR (CDCl3):
δ -109.39 (s, 2F). MS m/z (rel intens): 200 (M+, 5.40), 181
(7.39), 171 (5.68), 151 (10.37), 144 (100.00), 115 (70.31). Anal.
Calcd for C11H14F2O: C, 65.99; H, 7.05; F, 18.98. Found: C,
65.74; H, 6.98; F, 17.49.
(5) Tr iflu or om eth yla tion Rea ction of 3,3-Diflu or o-1-
iod ocyclop r op en es. (a ) Typ ica l Exp er im en ta l P r oce-
d u r e. Under nitrogen atmosphere, in a 10 mL side Pyrex tube
with a magnetic stirring bar was placed 4a (0.56 g, 2.0 mmol),
CuI (46 mg, 0.24 mmol), dimethylformamide (DMF; 1 mL), and
FSO2CF2COOMe (0.78 g, 4.0 mmol); the mixture was stirred
and heated at about 80 °C for 6 h and traced by 19F NMR.
After the reaction was complete, the mixture was cooled to
room temperature, poured into water (5 mL), and extracted
with ether (2 × 10 mL). The organic layer was dried over Na2-
SO4. After removal of solvent under reduced pressure, the
residue was purified by flash chromatography on a silica gel
column. 3,3-Difluoro-1-pehenyl-2-trifluoromethylcyclopropenes
(7a ; 0.20 g, 45%) was obtained as a colorless liquid (eluent:
petroleum ether).
(b) Com p ou n d 7a . Colorless liquid. IR (film; cm-1): 1803,
1609, 1513, 1367, 1334, 1170, 1066. 1H NMR(CDCl3): δ 7.69-
7.88 (m, 5H). 19F NMR (CDCl3): δ -103.49 (d, 2F), -55.14 (d,
3F). MS m/z (rel intens): 220 (M+, 35.79), 201 (13.34), 169
(11.84), 151 (100.00), 69 (10.13). HRMS. Calcd for C9H5F5:
220.0311. Found: 220.0264.
(c) Com p ou n d 7b. Colorless liquid. IR (film; cm-1): 2934,
2849, 1799, 1606, 1515, 1333, 1303, 1266, 1163, 1060. 1H NMR
(CDCl3): δ 3.90 (s, 3H), 7.01-7.05 (m, 2H), 7.65-7.69 (m, 2H).
19F NMR (CDCl3): δ -107.80 (d, 2F), -59.01 (d, 3F). MS m/z
(rel intens): 250 (M+, 100.00), 231 (26.22), 200 (31.00), 181
(99.76), 69 (7.70). Anal. Calcd for C10H7F5O: C, 52.81; H, 2.82;
F, 37.97. Found: C, 51.93; H, 2.45; F, 38.19.
(d ) Com p ou n d 7c. Colorless liquid. IR (film; cm-1): 1801,
1609, 1513, 1367, 1334, 1305, 1170, 1066. 1H NMR (CDCl3): δ
2.56 (s, 3H), 7.26-7.36 (m, 2H), 7.60-7.65 (m, 2H). 19F NMR
(CDCl3): δ -105.92 (s, 2F), -59.20 (s, 3F). MS m/z (rel
intens): 234 (M+, 56.14), 215 (8.49), 200 (3.62), 165 (100.00),
115 (9.57), 69 (2.75). HRMS. Calcd for C11H7F5: 234.0468.
Found: 234.0460.
(e) Com p ou n d 7d . Colorless liquid. IR (film; cm-1): 2964,
2935, 1806, 1595, 1492, 1332, 1171, 1095, 1072, 1017. 1H NMR
(CDCl3): δ 7.53-7.57 (m, 2H), 7.65-7.69 (m, 2H). 19F NMR
(CDCl3): δ -105.13 (t, 2F), -55.73 (d, 3F). MS m/z (rel
intens): 254 (M+, 50.81), 235 (13.17), 219 (27.23), 185 (100.00),
150 (17.88), 69 (13.63). HRMS. Calcd for C10H4ClF5: 253.9922.
Found: 253.9952.
(f) Com p ou n d 7e. Colorless liquid. IR (film; cm-1): 2965,
2839, 1815, 1452, 1336, 1159, 1067. 1H NMR(CDCl3): δ 0.90-
0.95 (m, 3H), 1.30-1.39 (m, 4H), 1.61-1.68 (m, 2H), 2.47-
2.54 (m, 2H). 19F NMR (CDCl3): δ -106.19 (s, 2F), -60.79 (s,
3F). MS m/z (rel intens): 195 (M+ - F, 0.51), 171 (14.81), 158
(100.00), 145 (18.06), 69 (13.63), 41 (56.08). Anal. Calcd for
C9H11F5: C, 50.46; H, 5.19; F, 44.35. Found: C, 50.14; H, 5.33;
F, 43.76.
(g) Com p ou n d 7f. Colorless liquid. IR (film; cm-1): 2930,
2859, 1815, 1468, 1336, 1159, 1070. 1H NMR (CDCl3): δ 0.86-
0.90 (m, 3H), 1.27 (s, 12H), 1.64-1.71 (m, 2H), 2.61-2.66 (m,
2H). 19F NMR (CDCl3): δ -103.11 (s, 2F), -60.80 (s, 3F). MS
m/z (rel intens): 265 (M+ - F, 0.70), 241 (0.77), 158 (19.14),
69 (58.79), 43 (100.00). Anal. Calcd for C14H21F5: C, 59.13;
H,7.46; F, 33.41. Found: C, 58.98; H, 7.37; F, 33.38.
(6) Hyd r olysis of 3,3-Diflu or o-1-iod o-2-p h en ylcyclo-
p r op en e (4a ). (a ) Typ ica l Exp er im en ta l P r oced u r e for
th e Hyd r olysis of 3,3-Diflu or o-1-iod o-2-p h en ylcyclop r o-
p en e u n d er Acid ic Con d ition s. A 10 mL flask with a water
condenser and a magnetic stirring bar was charged with 4a
(0.76 g, 2.75 mmol) and 5 mL of 2 N HCl, and the mixture
(i) Com p ou n d 6ec. Pale yellow liquid. IR (film; cm-1):
2961, 2935, 2865, 1784, 1699, 1681, 1607, 1423, 1363, 1318,
1250, 1180, 1041. 1H NMR (CDCl3): δ 0.91-0.93 (m, 3H),
1.32-1.41 (m, 4H), 1.63-1.73 (m, 2H), 2.37 (s, 3 H), 2.55-
2.62 (m, 3H), 6.59 (d, J ) 16.2 Hz, 1H), 7.03 (d t, J ) 15.9, 2.7
Hz, 1H). 19F NMR (CDCl3): δ -110.43 (s, 2F). MS m/z (rel
intens): 214 (M+, 1.83), 199 (1.25), 195 (6.44), 158 (21.43), 115
(11.76), 107 (15.16), 43 (100.00). 82). Anal. Calcd for C12H16F2O:
C, 67.27; H,7.53; F, 17.73. Found: C, 67.10; H, 6.98; F, 17.63.
(j) Com p ou n d 6ia . Yellow solid. IR (film; cm-1): 2958,
1773, 1630, 1585, 1488, 1436, 1365, 1311, 1294, 1175, 1067,
1
1062. H NMR (CDCl3): δ 3.85 (s, 3H), 6.54 (d, J ) 15.9 Hz,
1H), 7.47 (dt, J ) 15.9, 2.4 Hz, 1H), 7.51-7.55 (m, 2H), 7.64-
7.67 (m, 2H). 19F NMR (CDCl3): δ -113.64 (s, 2F). MS m/z
(rel intens): 316 (M+ + 2, 20.21), 314 (M+, 20.33), 299 (25.41),
255 (26.75), 235 (14.42), 220 (100.00), 192 (56.26), 155 (6.52).
Anal. Calcd for C13H9BrF2O2: C, 49.55; H, 2.88; F, 12.06.
Found: C, 49.76; H, 3.03; F, 12.17.
(k ) Com p ou n d 6ib. Yellow solid. IR (film; cm-1): 2994,
2826, 1767, 1721, 1690, 1583, 1487, 1365, 1313, 1282, 1228,
1012. 1H NMR (CDCl3): δ 6.69 (m, 1H), 7.28 (d t, J ) 15.9,
2.1 Hz, 1H), 7.54-7.69 (m, 4H), 9.81 (d, J ) 7.5 Hz, 1H). 19F
NMR (CDCl3): δ -112.47 (s, 2F). MS m/z (rel intens): 286
(M+ + 2, 53.71), 284 (M+, 56.37), 264 (9.88), 255 (29.90), 234
(25.50), 206 (40.52), 177 (100.00). Anal. Calcd for C12H7-
BrF2O: C, 50.56; H, 2.47; F, 13.33. Found: C, 50.62; H, 2.69;
F, 13.09.
(l) Com p ou n d 6ic. Yellow solid. IR (film; cm-1): 3095,
3028, 1766, 1695, 1609, 1583, 1488, 1368, 1299, 1253,1173,
1067, 1024. 1H NMR (CDCl3): δ 2.42 (s, 3H), 6.76 (d, J ) 15.9
Hz, 1H), 7.25 (d t, J ) 15.9, 2.4 Hz, 1H), 7.52-7.56 (m, 2H),
7.64-7.68 (m, 2H). 19F NMR (CDCl3): δ -113.64 (s, 2F). MS
m/z (rel intens): 300 (M+ + 2, 38.20), 298 (M+, 38.65), 284
(20.96), 255 (30.60), 229 (3.41), 191 (9.99), 155 (14.11). Anal.
Calcd for C13H9BrF2O: C, 52.20; H, 3.03; F, 12.70. Found: C,
52.38; H, 3.09; F, 12.63.
(m ) Com p ou n d 6ja . Pale brown solid. IR (film; cm-1):
3087, 1717, 1631, 1517, 1442, 1340, 1312, 1262, 1201, 1180,
1
1041. H NMR (CDCl3): δ 3.87 (s, 3H), 6.62 (d, J ) 15.9 Hz,
1H), 7.43 (dt, J ) 15.6, 2.7 Hz, 1H), 7.82-7.87 (m, 2H), 8.35-
8.40 (m, 2H). 19F NMR (CDCl3): δ -109.48 (s, 2F). MS m/z
(rel intens): 281 (M+, 26.54), 266 (100.00), 249 (15.79), 222
(31.07), 192 (38.61). Anal. Calcd for C13H9F2NO4: C, 55.52; H,
3.23; N, 4.98; F, 13.51. Found: C, 55.53; H, 3.28; N, 4.87; F,
13.50.
(n ) Com p ou n d 6jb. Pale brown solid. IR (film; cm-1): 3109,
2832, 1764, 1682, 1601, 1519, 1347, 1278, 1136, 1047. 1H NMR
(CDCl3): δ 6.77-6.84 (m,1H), 7.34 (d t, J ) 15.9, 2.1 Hz, 1H),
7.87 (d, J ) 8.7 Hz, 2H), 8.40 (d, J ) 6.9 Hz, 2H), 9.85 (d, J )
7.2 Hz, 1H). 19F NMR (CDCl3): δ -112.93 (s, 2F). MS m/z (rel
intens): 251 (M+, 34.76), 232 (2.17), 222 (6.14), 204 (11.72),
175 (28.05), 43 (100.00). Anal. Calcd for C12H7F2NO3: C, 57.38;
H, 2.81; N, 5.58; F, 15.13. Found: C, 57.34; H, 3.19; N, 5.53;
F, 15.31.
9426 J . Org. Chem., Vol. 67, No. 26, 2002