4308
F.-Y. Tsai et al. / Tetrahedron 63 (2007) 4304–4309
21 1
(
added), THF (20 mL) and Grignard reagent (15.0 mmol).
The mixture was stirred at 50 C or under refluxing con-
12.0 mmol; for aryl bromide, 1.2ꢂ10ꢁ2 mmol of PPh was
4.4.9. 2-Methoxybiphenyl. Colourless oil. H NMR
(CDCl , 400 MHz) d 3.84 (s, 3H), 7.00–7.10 (m, 2H),
3
3
ꢀ
7.34–7.38 (m, 3H), 7.43–7.47 (m, 2H), 7.57–7.59 (m, 2H);
C NMR (CDCl , 100 MHz) d 55.6, 110.9, 120.4, 126.5,
3
127.6 (2C), 128.2, 129.1 (2C), 130.2, 130.4, 138.0, 155.8.
1
3
ditions. After cooling to room temperature, 3 N HCl was
added and extracted with EtOAc. The organic layer was
dried over MgSO and the solvent was removed under
4
2
7
vacuum. Column chromatography on silica gel afforded
the desired product.
4.4.10. 2-(2-Methoxyphenyl)thiophene. Pale yellow oil.
H NMR (CDCl , 400 MHz) d 3.94 (s, 3H), 6.99–7.04
1
3
(
m, 2H), 7.10–7.13 (m, 1H), 7.24–7.30 (m, 1H), 7.33–7.35
ꢀ
EtOH (lit. 89 C). H NMR (CDCl , 400 MHz) d 3.85 (s,
13
4
.4.1. 4-Methoxybiphenyl. White solid. Mp 85–87 C from
ꢀ
(m, 1H), 7.52–7.54 (m, 1H), 7.68 (d, J¼8.0 Hz, 1H); C
NMR (CDCl , 100 MHz) d 55.6, 111.2, 120.5, 122.9,
2
1
1
3
3
3
7
1
H), 6.95 (d, J¼6.8 Hz, 2H), 7.30–7.32 (m, 1H), 7.40–
124.9, 125.0, 126.4, 127.9, 128.1, 138.9, 154.9.
1
3
.43 (m, 2H), 7.51–7.55 (m, 4H); C NMR (CDCl ,
3
0
00 MHz) d 55.5, 113.9 (2C), 126.3, 126.4 (2C), 127.7
4.4.11. 4 -Methoxy-2,4,6-trimethylbiphenyl. Mp 73–
ꢀ
28
ꢀ
1
(
2C), 128.3 (2C), 133.3, 140.3, 158.5.
75 C from EtOH (lit. 74–75 C). H NMR (CDCl3,
00 MHz) d 2.04 (s, 6H), 2.35 (s, 3H), 3.87 (s, 3H), 6.95–
6.99 (m, 4H), 7.05–7.08 (m, 2H); C NMR (CDCl3,
100 MHz) d 21.2 (2C), 21.4, 55.3, 113.4 (2C), 127.6 (2C),
129.98 (2C), 132.8, 136.0, 138.2, 157.5.
4
ꢀ
EtOH (lit. 35 C). H NMR (CDCl , 400 MHz) d 7.07–
13
4
.4.2. 2-Phenylthiophene. White solid. Mp 35–36 C from
2
1
ꢀ
.09 (m, 1H), 7.26–7.32 (m, 3H), 7.36–7.40 (m,
1
3
7
2
1
3
H), 7.61–7.63 (m, 2H); C NMR (CDCl , 100 MHz)
3
ꢀ
d 122.7, 124.4, 125.6 (2C), 127.0, 127.6, 128.5 (2C),
1
4.4.12. 4-Chlorobiphenyl. White solid. Mp 74–76 C from
EtOH (lit. 75–77 C). H NMR (CDCl , 400 MHz) d 7.34–
2
4
ꢀ
.45 (m, 5H), 7.50–7.56 (m, 4H); C NMR (CDCl3,
1
33.9, 143.9.
3
1
3
7
100 MHz) d 126.6 (2C), 127.2, 128.3 (2C), 128.5 (2C),
128.6 (2C), 132.9, 139.2, 139.5.
ꢀ
4
.4.3. Biphenyl. White solid. Mp 71–72 C from EtOH
ꢀ
2
2
1
(
(
lit. 70–71 C). H NMR (CDCl , 400 MHz) d 7.20–7.75
3
m, 10H); C NMR (CDCl , 100 MHz) d 126.8 (2C),
3
1
3
1
26.9 (4C), 128.3 (4C), 140.8 (2C).
4.4.13. 2-(4-Chlorophenyl)thiophene. White solid. Mp 83–
8
ꢀ ꢀ
4 C from EtOH (lit. 81–82.5 C). H NMR (CDCl ,
3
29
1
2
3 1
4
4
1
7
1
1
.4.4. Styrene. Colourless liquid.
H NMR (CDCl3,
400 MHz) d 7.05–7.08 (m, 1H), 7.27–7.28 (m, 2H), 7.33
(d, J¼8.0 Hz, 2H), 7.52 (d, J¼8.0 Hz, 2H); C NMR
1
3
00 MHz) d 5.30 (d, J¼10.8 Hz, 1H), 5.81 (d, J¼17.6 Hz,
H), 6.78 (dd, J¼10.8, 17.6 Hz, 1H), 7.29–7.30 (m, 1H),
(CDCl , 100 MHz) d 123.1, 124.8, 126.7, 127.7 (2C),
3
1
3
.32–7.40 (m, 2H), 7.46–7.48 (m, 2H); C NMR (CDCl ,
3
128.6 (2C), 132.5, 132.7, 142.6.
00 MHz) d 113.5, 125.8 (2C), 127.4, 128.1 (2C), 136.4,
37.0.
0
4.4.14. 4 -Chloro-4-methoxybiphenyl. White solid. Mp
ꢀ
ꢀ
30
1
1
14–115 C from EtOH (lit. 113–114 C). H NMR
ꢀ
EtOH (lit. 44.5–46.5 C). H NMR (CDCl , 400 MHz)
4
.4.5. 4-Methylbiphenyl. White solid. Mp 43–45 C from
(CDCl , 400 MHz) d 3.84 (s, 3H), 6.96 (d, J¼8.4 Hz, 2H),
3
2
4
ꢀ
d 2.42 (s, 3H), 7.24–7.28 (m, 2H), 7.32–7.36 (m, 1H),
1
13
7.36 (d, J¼8.8 Hz, 2H), 7.44–7.48 (m, 4H); C NMR
3
(CDCl , 100 MHz) d 55.5, 114.0 (2C), 127.5 (2C), 127.6
3
7
2
.42–7.51 (m, 2H), 7.51–7.53 (m, 2H), 7.58–7.61 (m,
H); C NMR (CDCl , 100 MHz) d 21.5, 126.6, 128.3
(2C), 128.4, 132.2 (2C), 132.6, 138.8, 158.7.
1
3
3
0 ꢀ
4.4.15. 2,2 -Bithienyl. White solid. Mp 32–34 C from
(
1
2C), 128.4 (2C), 129.0 (2C), 129.1 (2C), 136.5, 137.9,
40.6.
3
1
ꢀ
EtOH (lit. 33 C). H NMR (CDCl , 400 MHz) d 7.01–
3
1
1
3
7.04 (m, 2H), 7.19–7.22 (m, 4H); C NMR (CDCl3,
100 MHz) d 123.4 (2C), 124.0 (2C), 127.3 (2C), 136.9 (2C).
ꢀ
EtOH (lit. 63–64 C). H NMR (CDCl , 400 MHz) d 2.37
4
.4.6. 2-p-Tolylthiophene. White solid. Mp 67–69 C from
ꢀ
2
5
1
3
ꢀ
EtOH (lit. 89 C). H NMR (CDCl , 400 MHz) d 7.29–
(
7
1
s, 3H), 7.05–7.07 (m, 1H), 7.18 (d, J¼7.8 Hz, 2H), 7.23–
4.4.16. 3-Phenylthiophene. White solid. Mp 89–91 C from
ꢀ
1
3
32
1
.27 (m, 2H), 7.50 (d, J¼7.8 Hz, 2H); C NMR (CDCl ,
3
3
00 MHz) d 21.6, 122.2, 123.9, 125.5 (2C), 127.5, 129.1
7.33 (m, 1H), 7.38–7.44 (m, 4H), 7.46–7.47 (m, 1H),
7.60–7.63 (m, 2H); C NMR (CDCl , 100 MHz) d 119.9,
3
1
3
(
2C), 131.2, 136.9, 144.1.
1
25.8, 125.9, 126.0 (2C), 126.7, 128.4 (2C), 135.4, 141.8.
0
13–114 C from EtOH (lit. 109–110 C). H NMR
4
1
(
.4.7. 4 -Methoxy-4-methylbiphenyl. White solid. Mp
ꢀ
CDCl , 400 MHz) d 2.38 (s, 3H), 3.84 (s, 3H), 6.95 (d,
26
ꢀ
1
0 ꢀ
4.4.17. 2,3 -Bithienyl. Brown crystal. Mp 62–64 C from
EtOH (lit. 65 C). H NMR (CDCl , 400 MHz) d 7.03–
3
1
ꢀ
1
3
3
J¼8.8 Hz, 2H), 7.21 (d, J¼8.0 Hz, 2H), 7.44 (d, J¼8.0 Hz,
7.05 (m, 1H), 7.20–7.22 (m, 2H), 7.31–7.35 (m, 2H),
7.38–7.39 (m, 1H); C NMR (CDCl , 100 MHz) d 119.2,
122.8, 123.5, 125.8, 125.9, 127.3, 135.1, 138.6.
1
3
13
2
d 21.5, 55.5, 113.8 (2C), 126.2 (2C), 127.6 (2C), 129.0
H), 7.50 (d, J¼8.8 Hz, 2H); C NMR (CDCl , 100 MHz)
3
3
(
2C), 133.3, 135.9, 137.5, 158.3.
4
130–132 C from EtOH (lit. 127 C). H NMR (CDCl ,
.4.18. 3-(4-Methoxyphenyl)thiophene. White solid. Mp
ꢀ
0
80 C from EtOH (lit. 178–179 C). H NMR (CDCl ,
ꢀ
33
1
4
1
4
.4.8. 4,4 -Dimethoxybiphenyl. Pale yellow solid. Mp 178–
ꢀ
3
26
ꢀ
1
400 MHz) d 3.83 (s, 3H), 6.92 (d, J¼6.4 Hz, 2H), 7.32–
3
1
3
00 MHz) d 3.84 (s, 6H), 6.96 (d, J¼8.8 Hz, 4H), 7.48 (d,
7.35 (m, 3H), 7.51 (d, J¼6.4 Hz, 2H); C NMR (CDCl ,
3
1
3
J¼8.8 Hz, 4H); C NMR (CDCl , 100 MHz) d 55.5 (2C),
100 MHz) d 55.5, 113.9, 118.6 (2C), 125.7, 125.8, 127.1
(2C), 128.3, 141.5, 158.2.
3
1
14.4 (4C), 127.3 (4C), 133.0 (2C), 158.0 (2C).