PAPER
Homocoupling Reaction of Arylboronic Acids
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4,4¢-Dimethoxybiphenyl (2c)
1H NMR (400 MHz, CDCl3): d = 7.27–7.20 (6 H, m), 7.10 (2 H, d,
J = 7.0 Hz), 2.05 (6 H, s).
White solid; mp 173–175 °C (Lit.5a mp 173–174 °C).
1H NMR (400 MHz, CDCl3): d = 7.48 (4 H, d, J = 8.8 Hz), 6.96 (4
H, d, J = 8.8 Hz), 3.84 (6 H, s).
13C NMR (100 MHz, CDCl3): d = 141.7, 135.9, 129.9, 129.4, 127.2,
125.6, 19.9.
13C NMR (100 MHz, CDCl3): d = 158.8, 133.6, 127.8, 114.3, 55.4.
EI-MS: m/z = 214 (M+).
EI-MS: m/z = 182 (M+).
3,3¢-5,5¢-Tetrafluorobiphenyl (2k)
White solid; mp 82–84 °C (Lit.13 mp 85.5–87 °C).
4,4¢-Dimethylbiphenyl (2d)
White solid; mp 118–120 °C (Lit.5a mp 122–124 °C).
1H NMR (400 MHz, CDCl3): d = 7.09–7.03 (4 H, m), 6.89 (2 H, tt,
J = 8.8, 2.3 Hz).
13C NMR (100 MHz, CDCl3): d = 163.2 (dd, J = 247.6, 13.1 Hz),
142.2 (t, J = 11.9 Hz), 110.3 (d, J = 26.2 Hz), 103.4 (t, J = 25.4 Hz).
1H NMR (400 MHz, CDCl3): d = 7.48 (4 H, d, J = 7.9 Hz), 7.24 (4
H, d, J = 7.9 Hz), 2.39 (6 H, s).
13C NMR (100 MHz, CDCl3): d = 138.4, 136.8, 129.5, 126.9, 21.2.
EI-MS: m/z = 182 (M+).
EI-MS: m/z = 226 (M+).
1,1¢-Binaphthyl (2m)
4,4¢-Biphenyldicarboxyaldehyde (2e)
White solid; 142–144 °C (Lit.15 mp 141–143 °C).
White solid; mp 150–151 °C (Lit.5a mp 148–150 °C).
1H NMR (400 MHz, CDCl3): d = 7.97–7.94 (4 H, m), 7.62–7.58 (2
H, m), 7.51–7.46 (4 H, m), 7.42–7.37 (2 H, m), 7.27–7.24 (2 H, m).
13C NMR (100 MHz, CDCl3): d = 138.5, 133.6, 132.9, 128.2, 128.0,
127.9, 126.6, 125.9, 125.7, 125.5.
1H NMR (400 MHz, CDCl3): d = 10.0 (2 H, s), 8.01 (4 H, d, J = 8.3
Hz), 7.81 (4 H, d, J = 8.3 Hz).
13C NMR (100 MHz, CDCl3): d = 191.8, 145.6, 136.0, 130.4, 128.1.
EI-MS: m/z = 210 (M+).
EI-MS: m/z = 254 (M+).
3,3¢-Difluorobiphenyl (2f)
2,2¢-Binaphthyl (2n)
Colorless liquid.12
White solid; mp 184–186 °C (Lit.15 mp 188 °C).
1H NMR (400 MHz, CDCl3): d = 7.44–7.34 (4 H, m), 7.28–7.24 (2
H, m), 7.09–7.04 (2 H, m).
13C NMR (100 MHz, CDCl3): d = 163.2 (d, J = 244.6 Hz), 142.3
(dd, J = 7.7, 2.2 Hz), 130.5 (d, J = 8.0 Hz), 122.8 (d, J = 2.9 Hz),
114.8 (d, J = 21.0 Hz), 114.1 (d, J = 21.0 Hz).
1H NMR (400 MHz, CDCl3): d = 8.17 (2 H, s), 7.97–7.92 (4 H, m),
7.90–7.87 (4 H, m), 7.54–7.47 (4 H, m).
13C NMR (100 MHz, CDCl3): d = 138.5, 133.8, 132.8, 128.6, 128.4,
127.8, 126.5, 126.2, 126.1, 125.8.
EI-MS: m/z = 254 (M+).
EI-MS: m/z = 190 (M+).
3,3¢-Bithiophene (2o)
3,3¢-Dinitrobiphenyl (2g)
White solid; mp 130–131 °C (Lit.17 mp 130 °C).
Yellow solid; mp 201–202 °C (Lit.5a mp 201–202 °C).
1H NMR (400 MHz, CDCl3): d = 7.39 (2 H, d, J = 1.4 Hz,), 7.38–
7.33 (4 H, m).
13C NMR (100 MHz, CDCl3): d = 137.3, 126.5, 126.2, 119.9.
EI-MS: m/z = 166 (M+).
1H NMR (400 MHz, CDCl3): d = 8.51 (2H, t, J = 1.9 Hz), 8.31 (2H,
dq, J = 8.2, 1.9 Hz), 7.98 (2H, dq, J = 8.2, 1.9 Hz), 7.72 (2H, t,
J = 8.2 Hz).
13C NMR (100 MHz, CDCl3): d = 148.9, 140.3, 133.1, 130.3, 123.3,
122.1.
2,2¢-Bibenzofuran (2p)
EI-MS: m/z = 244 (M+).
White solid; mp 197–199 °C (Lit.5a mp 198–200 °C).
2,2¢-Difluorobiphenyl (2h)
1H NMR (400 MHz, CDCl3): d = 7.65–7.63 (2 H, m), 7.56–7.54 (2
H, m), 7.35 (2 H, dt, J = 7.3, 1.4 Hz), 7.28 (2 H, dt, J = 7.3, 0.9 Hz),
7.18 (2 H, s).
13C NMR (100 MHz, CDCl3): d = 155.2, 147.8, 128.6, 125.2, 123.5,
121.5, 111.4, 103.8.
White solid; mp 118–120 °C (Lit.18 mp 117–118 °C).
1H NMR (400 MHz, CDCl3): d = 7.41–7.35 (4 H, m), 7.24–7.15 (4
H, m).
13C NMR (100 MHz, CDCl3): d = 159.9 (dd, J = 248.6, 13.1 Hz),
131.7 (t, J = 2.6 Hz), 129.9 (t, J = 4.0 Hz), 124.2 (d, J = 2.2 Hz),
115.9 (d, J = 6.4 Hz), 115.6 (d, J = 6.4 Hz).
EI-MS: m/z = 234 (M+).
(1E,3E)-1,4-Diphenylbuta-1,3-diene (2q)
EI-MS: m/z = 190 (M+).
White solid; mp 150–152 °C (Lit.16 mp 151–152 °C).
3,3¢-Dichlorobiphenyl (2i)
1H NMR (400 MHz, CDCl3): d = 7.47–7.45 (4 H, m), 7.36–7.32 (4
H, m), 7.28–7.24 (2 H, m), 6.99–6.93 (2 H, m), 6.72–6.66 (2 H, m).
White solid; mp 59–62 °C (Lit.5a mp 57–58 °C).
1H NMR (400 MHz, CDCl3): d = 7.50–7.47 (2 H, m), 7.37–7.33 (4
H, m), 7.30–7.26 (2 H, m).
13C NMR (100 MHz, CDCl3): d = 137.4, 132.9, 129.3, 128.7, 127.6,
126.5.
13C NMR (100 MHz, CDCl3): d = 138.5, 133.6, 131.3, 129.6, 129.2,
126.7.
EI-MS: m/z = 206 (M+).
EI-MS: m/z = 222 (M+).
Acknowledgment
2,2¢-Dimethylbiphenyl (2j)
The Japan Society for the Promotion of Science (JSPS) is thanked
for supporting this work. B. K. thanks the JSPS for a fellowship.
This work was partially supported by a grant for private universities
Colorless liquid.5a
Synthesis 2011, No. 1, 91–96 © Thieme Stuttgart · New York