P. Gomes et al. / Tetrahedron 58 (2002) 8417–8424
8423
4H), 4.39 (q, CH2, J¼7.1 Hz), 3.81 (s, OMe), 1.40 (t, CH3,
J¼7.1 Hz); 13C NMR (50 MHz) d (ppm): 166.3, 156.2,
143.1, 130.5, 129.1, 126.9, 120.7, 111.1, 60.6, 55.3, 14.2;
MS, m/z (%): 257 (16) [Mþ1], 256 (99) [Mþ], 228 (31), 212
(15), 211 (100), 183 (13), 169 (17), 168 (55), 139 (18).
J¼8.2 Hz), 6.94 (dd, 2H, J¼8.8, 1.9 Hz), 3.80 (s, 3H, OMe),
2.66 (q, CH2, J¼7.6 Hz), 1.25 (t, CH3, J¼7.6 Hz); 13C NMR
(50 MHz) d (ppm): 159.0, 142.8, 138.3, 133.8, 128.3, 128.1,
126.7, 114.2, 55.4, 28.6, 15.7; MS, m/z (%): 212 (68) [Mþ],
198 (14), 197 (100), 182 (13), 154 (22).
3.2.3. 30-Methoxy-biphenyl-4-carboxylic acid ethyl ester
3.2.10. Biphenyl-2,40-dicarboxylic acid 40-ethyl ester
1
1
3.31 Yield: 72%; H NMR (200 MHz) d (ppm): 8.10 (dd,
2-methyl ester 10.36 Yield: 82%; H NMR (200 MHz) d
2H, J¼8.5, 1.8 Hz), 7.64 (dd, 2H, J¼8.5, 1.8 Hz), 7.37–
7.13 (m, 3H), 6.96–6.90 (m, 1H), 4.39 (q, CH2, J¼7.1 Hz),
3.86 (s, OMe), 1.41 (t, CH3, J¼7.1 Hz); 13C NMR (50 MHz)
d (ppm): 166.3, 159.9, 145.2, 141.4, 129.8, 129.2, 126.9,
119.6, 113.3, 112.9, 60.8, 55.2, 14.2; MS, m/z (%): 257 (17)
[Mþ1], 256 (96) [Mþ], 228 (53), 212 (21), 211 (100), 183
(12), 168 (28), 153 (15), 152 (12), 140 (12), 139 (16).
(ppm): 8.20–7.36 (m, 8H), 4.42 (q, CH2, J¼7.1 Hz), 3.68 (s,
COOMe) 1.44 (t, CH3, J¼7.1 Hz); 13C NMR (50 MHz) d
(ppm): 168.4, 166.3, 145.9, 141.5, 131.4, 130.4, 130.0,
129.1, 128.2, 127.7, 127.0, 60.8, 51.9, 14.2; MS, m/z (%):
284 (99) [Mþ], 256 (41), 253 (22), 239 (100), 225 (31), 181
(70), 152 (23).
3.2.11. 20-Cyano-biphenyl-4-carboxylic acid ethyl ester
11. Yield: 79%; 1H NMR (200 MHz) d (ppm): 8.09 (dd, 2H,
J¼8.3, 1.8 Hz), 7.73–7.37 (m, 6H), 4.42 (q, CH2,
J¼7.1 Hz), 1.42 (t, CH3, J¼7.1 Hz); 13C NMR (50 MHz)
d (ppm): 166.1, 144.3, 142.3, 132.9, 130.7, 130.0, 128.2,
118.2, 111.3, 61.1, 14.4; MS, m/z (%): 251 (38) [Mþ], 228
(13), 223 (91), 207 (18), 206 (100), 179 (47), 178 (42), 177
(20), 151 (44), 150 (22). Anal. calcd for C16H13NO2: C,
76.48; H, 5.21; N, 5.57. Found: C, 76.45; H, 5.18; N, 5.63.
3.2.4. 40-Methoxy-biphenyl-4-carboxylic acid ethyl ester
4.32 Yield: 88%; 1H NMR (200 MHz) d (ppm): 8.08 (d, 2H,
J¼8.4 Hz), 7.61 (d, 2H, J¼8.4 Hz), 7.57 (d, 2H, J¼8.8 Hz),
6.98 (d, 2H, J¼8.8 Hz), 4.39 (q, CH2, J¼7.1 Hz), 3.85 (s,
OMe), 1.41 (t, CH3, J¼7.1 Hz); 13C NMR (50 MHz) d
(ppm): 166.3, 159.6, 144.9, 132.2, 129.8, 128.1, 126.2,
114.1, 60.7, 55.1, 14.1; MS, m/z (%): 257 (22) [Mþ1], 256
(100) [Mþ], 228 (54), 211 (76), 168 (26).
3.2.5. 20-Methoxy-biphenyl-2-carboxylic acid methyl
3.2.12. 40-Cyano-biphenyl-4-carboxylic acid ethyl ester
1
1
ester 5.33 Yield: 90%; H NMR (200 MHz) d (ppm): 7.89
12.37 Yield: 68%; H NMR (200 MHz) d (ppm): 8.14 (dd,
(d, 1H, J¼8.2 Hz), 7.55–6.86 (m, 7H), 3.66 (s, 3H,
COOMe), 3.63 (s, 3H, OMe); 13C NMR (50 MHz) d
(ppm): 168.5, 156.1, 138.9, 131.5, 131.2, 130.4, 129.8,
129.2, 128.7, 126.9, 120.8, 110.2, 55.1, 51.5; MS, m/z (%):
242 (34) [Mþ], 211 (100), 196 (39), 168 (24), 149 (22).
2H, J¼8.5, 1.6 Hz), 7.77–7.63 (m, 6H), 4.23 (q, CH2,
J¼7.1 Hz), 1.42 (t, CH3, J¼7.1 Hz); 13C NMR (50 MHz) d
(ppm): 165.9, 144.2, 143.1, 132.5, 130.4, 130.1, 127.7,
127.0, 118.5, 111.6, 61.0, 14.2; MS, m/z (%): 251 (46) [Mþ],
223 (66), 206 (100), 178 (27), 177 (22), 151 (35).
3.2.6. 40-Methoxy-biphenyl-2-carbonitrile 6.34 Yield:
81%; H NMR (200 MHz) d (ppm): 7.75–6.91 (m, 8H),
3.84 (s, 3H, OMe); 13C NMR (50 MHz) d (ppm): 160.0,
145.2, 133.7, 132.7, 130.5, 130.0, 129.9, 127.0, 119.0,
114.1, 111.0, 55.2; MS, m/z (%): 210 (16) [Mþ1], 209 (100)
[Mþ], 194 (37), 180 (12), 179 (10), 167 (11), 166 (70), 140
(20), 139 (13).
3.2.13. 30-Chloro-biphenyl-4-carboxylic acid ethyl ester
13. Yield: 52%; 1H NMR (200 MHz) d (ppm): 7.95 (dd, 2H,
J¼8.4, 1.7 Hz), 7.44 (dd, 2H, J¼8.4, 1.7 Hz), 7.34–7.17 (m,
1
4H), 4.26 (q, CH2, J¼7.1 Hz), 1.27 (t, CH3, J¼7.1 Hz); 13
C
NMR (50 MHz) d (ppm): 166.1, 143.7, 141.6, 134.7, 130.0,
129.7, 127.9, 127.2, 127.1, 126.9, 125.2, 60.9, 14.1; MS, m/z
(%): 262 (23) [Mþ], 260 (69) [Mþ], 234 (18), 232 (67), 217
(35), 216 (15), 215 (97), 153 (14), 152 (100), 151 (13). Anal.
calcd for C15H13ClO2: C, 69.10; H, 5.03. Found: C, 69.84;
H, 5.23.
3.2.7. 30-Trifluoromethyl-biphenyl-4-carboxylic acid
ethyl ester 7.30 Yield: 57%; 1H NMR (200 MHz) d
(ppm): 8.17–8.11 (m, 2H), 7.85–7.53 (m, 6H), 4.41 (q,
CH2, J¼7.1 Hz), 1.42 (t, CH3, J¼7.1 Hz); 13C NMR
(50 MHz) d (ppm): 166.1, 143.7, 140.7, 131.4 (q,
J¼32.5 Hz), 130.4, 130.1, 129.2, 126.9, 124.6, 124.0 (q,
J¼272.4 Hz), 60.9, 14.1; 19F NMR (50 MHz) d (ppm):
262.5 (3F, s); MS, m/z (%): 294 (57) [Mþ], 266 (59), 250
(17), 249 (100), 201 (32), 152 (17).
3.2.14. 40-Cyano-biphenyl-4-carboxylic acid methyl ester
1
14.38 Yield: 60%; H NMR (200 MHz) d (ppm): 8.14 (dd,
2H, J¼8.3, 1.7 Hz), 7.78–7.63 (m, 6H), 3.95 (s, COOMe);
13C NMR (50 MHz) d (ppm): 166.6, 144.4, 143.4, 132.7,
130.2, 127.9, 127.2, 118.7, 111.8, 52.3; MS, m/z (%): 237
(64) [Mþ], 207 (13), 206 (100), 178 (27), 177 (17), 151 (32).
3.2.8. 30-Trifluoromethyl-biphenyl-2-carbonitrile 8.
Yield: 81%; H NMR (200 MHz) d (ppm): 7.79–7.41 (m,
3.2.15. 4-Thiophen-3-yl-benzoic acid ethyl ester 15.39
Yield: 50%; H NMR (200 MHz) d (ppm): 7.96 (d, 2H,
1
1
8H); 13C NMR (50 MHz) d (ppm): 143.8, 139.0, 133.9,
133.2, 132.2, 131.2 (q, J¼32.6 Hz), 130.1, 129.4, 128.4,
125.5, 124.0 (q, J¼272.4 Hz), 118.3, 111.4; 19F NMR
(50 MHz) d (ppm): 262.3 (3F, s); MS, m/z (%): 248 (15)
[Mþ1], 247 (100) [Mþ], 228 (10), 227 (23), 226 (15), 208
(13), 182 (15), 177 (11). Anal. calcd for C14H8F3N: C,
68.02; H, 3.26; N, 5.67. Found: C, 67.90; H, 3.43; N, 5.79.
J¼8.4 Hz), 7.57 (d, 2H, J¼8.4 Hz), 7.44 (dd, 1H, J¼4.0,
2.0 Hz), 7.27 (m, 2H), 4.29 (q, CH2, J¼7.1 Hz), 1.30 (t,
CH3, J¼7.1 Hz); 13C NMR (50 MHz) d (ppm): 166.4,
141.2, 139.9, 130.1, 128.9, 126.6, 126.1, 121.8, 60.9, 14.3;
MS, m/z (%): 233 (17) [Mþ1], 232 (100) [Mþ], 205 (15),
204 (38), 187 (72), 159 (11), 115 (22).
3.2.16. 1-(4-Thiophen-3-yl-phenyl)-ethanone 16.39 Yield:
35%; 1H NMR (200 MHz) d (ppm): 8.00 (m, 2H), 7.68 (m,
2H), 7.58 (m, 1H), 7.44 (m, 2H), 2.62 (s, CH3); 13C NMR
0
1
3.2.9. 4 -Ethyl-4-methoxy-biphenyl 9.35 Yield: 65%; H
NMR (200 MHz) d (ppm): 7.53–7.44 (m, 4H), 7.23 (d, 2H,