Optimized general procedure for the Suzuki coupling (Table 4,
Entry 1)
280 ◦C, 10 min): tR = 18.6 min; m/z 193. 1H-NMR (200 MHz,
CDCl3) d = 2.41 (s, 3 H), 7.26–7.34 (m, 2 H) 7.35–7.54 (m,
4 H) 7.56–7.68 (m, 1 H) 7.74 (dd, J = 1.5/7.7Hz, 1 H). 13C-
NMR (50 MHz, CDCl3) d = 21.1, 103.7, 111.0, 127.1, 128.4,
129.3, 129.8, 132.6, 133.5, 135.1, 138.5, 145.3. Anal. Calcd for
C14H11N (193.24): C, 87.01; H, 5.74; N, 7.25. Found: C, 86.67;
H, 5.75; N, 7.27.
Reactions have to be conducted under argon. In the presence
of air, biphenyl, the homocoupling product of boronic acid, is
formed up to ~15%, while in the absence of air it is limited
to less than 2%.22 Complex 2 (14.5 mg, 0.01 mmol) is added
to [bmpy][NTf2] (1 mL) and the yellow solution is stirred at
65 ◦C for a few minutes. Phenylboronic acid (0.183 g, 1.5 mmol),
K3PO4 (0.424 g, 2 mmol) and degassed water (0.5 mL) are added
to the solution. After a few minutes, an orange homogeneous
solution is formed. 2-Methyl-bromobenzene (0.12 mL, 1 mmol)
is added to the reaction mixture and the solution is stirred at
65 ◦C for 2 h. After cooling to room temperature, the reaction
mixture is directly charged onto a silica gel column and the
desired product is isolated by elution with cyclohexane (0.155 g,
0.92 mmol, 92%).
2-Methyl-3◦¢-nitrobiphenyl (Table 4,◦Entry 7). GC-MS (50 ◦C,
2 min → 280 C, 10 ◦C min-1 → 280 C, 10 min): tR = 19.2 min;
m/z 213. 1H-NMR (300 MHz, CDCl3) d = 2.29 (s, 3 H), 7.21–
7.36 (m, 4 H), 7.55–7.70 (m, 2 H), 8.19–8.25 (m, 2 H). 13C-NMR
(75 MHz, CDCl3) d = 20.1, 121.6, 123.8, 126.0, 128.2, 128.9,
129.4, 130.5, 135.0, 135.2, 139.1, 143.3, 147.9. Anal. Calcd for
C13H11NO2 (213.23): C, 73.23; H, 5.20; N, 6.57. Found: C, 73.16;
H, 5.21; N, 6.55.
1-(4-Methoxyphenyl)naphthalene (Table 4, Entry◦8). m.p. =
2-Methylbip◦henyl (Table 4, Entry 1). GC-MS (50 ◦C, 2 min
→ 280 ◦C, 10 C min-1 → 280 ◦C, 10 min): tR = 14.1 min; m/z
168. 1H-NMR (300 MHz, CDCl3) d = 2.32 (s, 3 H), 7.25–7.50
(m, 10 H). 13C-NMR (75 MHz, CDCl3) d = 20.4, 125.7, 126.7,
127.2, 128.0, 129.10, 129.13, 129.7, 130.3, 135.2, 141.89, 141.92.
Anal. Calcd for C13H12 (168.23): C, 92.81; H, 7.19. Found: C,
92.55; H, 7.20.
◦
◦
◦
115–117 C. GC-MS (50 C, 2 min → 280 C, 10 C min-1
→
280 ◦C, 10 min): tR = 22.1 min; m/z 234. 1H-NMR (300 MHz,
CDCl3) d = 3.91 (s, 3 H), 7.02–7.08 (m, 2 H), 7.39–7.56 (m, 6 H),
7.79–7.97 (m, 3 H). 13C-NMR (50 MHz, CDCl3) d = 55.3, 113.7,
125.4, 125.7, 125.9, 126.0, 126.9, 127.3, 128.2, 131.1, 131.8,
133.1, 133.8, 139.9, 158.9. Anal. Calcd for C17H14O (234.29):
C, 87.15; H, 6.02. Found: C, 87.35; H, 6.00.
4-Me◦thoxybiphenyl (Table 4, Entry 2). m.p. = 85–86 ◦C. GC-
MS (50 C, 2 min → 280 ◦C, 10 ◦C min-1 → 280 ◦C, 10 min): tR =
17.6 min; m/z 184. 1H-NMR (300 MHz, CDCl3) d = 3.87 (s, 3
H), 7.00 (d, J = 8.5 Hz, 2 H,), 7.32 (t, J = 7.3 Hz, 1 H), 7.43 (t, J =
7.6 Hz, 2 H), 7.49–7.62 (m, 4 H). 13C-NMR (75 MHz, CDCl3)
d = 55.3, 114.2, 126.6, 126.7, 128.1, 128.7, 133.7, 140.8, 159.1.
Anal. Calcd for C13H12O (184.23): C, 84.75; H, 6.57. Found: C,
84.53; H, 6.58.
4,◦4¢-dimethoxybip◦henyl (Table 4, Entry ◦9). m.p. = 178–
179 C. GC-MS (50 C, 2 min → 280 ◦C, 10 C min-1 → 280 ◦C,
10 min): tR = 20.1 min; m/z 214. 1H-NMR (200 MHz, CDCl3)
d = 3.86 (s, 6 H), 6.97 (d, J = 8.9 Hz, 4 H), 7.49 (d, J = 8.9 Hz,
4 H). 13C-NMR (50 MHz, CDCl3) d = 55.3, 114.1, 127.7, 133.4,
158.6. Anal. Calcd for C14H14O2 (214.26): C, 78.48; H, 6.59.
Found: C, 78.53; H, 6.58.
2,2¢-Dimethylbiphenyl (Table 4, E◦ntry 3). GC-MS (50 ◦C,
2 min → 280 ◦C, 10 ◦C min-1 → 280 C, 10 min): tR = 14.4 min;
m/z 182. 1H-NMR (300 MHz, CDCl3) d = 2.07 (s, 6 H), 7.08–
7.15 (m, 2 H), 7.18–7.33 (m, 6 H). 13C-NMR (50 MHz, CDCl3)
d = 19.8, 125.5, 127.1, 129.2, 129.8, 135.8, 141.6. Anal. Calcd
for C14H14 (182.26): C, 92.26; H, 7.74. Found: C, 92.43; H, 7.72.
4-Methoxy-4¢-phenylbiphenyl (Table 4, E◦ntry 10). m.p. =
222–223 ◦C. GC-MS (100 ◦C, 2 min → 280 C, 10 ◦C min-1
→
280 ◦C, 10 min): tR = 19.8 min; m/z 260. 1H-NMR (300 MHz,
CDCl3) d = 3.88 (s, 3 H), 7.01 (d, J = 8.8 Hz, 2 H), 7.32–
7.42 (m, 1 H) 7.43–7.52 (m, 2 H) 7.55–7.71 (m, 8 H). 13C-NMR
(75 MHz, CDCl3) d = 55.4, 114.3, 127.0, 127.0, 127.2, 127.5,
128.0, 128.8, 133.2, 139.5, 139.7, 140.8, 159.2. Anal. Calcd for
C19H16O (260.33): C, 87.66; H, 6.19. Found: C, 87.54; H, 6.17.
1-o-Tolylnaphtha◦lene (Table 4, Entry ◦ 4). m.p.
=
69–
70 ◦C. GC-MS (50 C, 2 min → 280 ◦C, 10 C min-1 → 280 ◦C,
10 min): tR = 19.6 min; m/z 218. 1H-NMR (300 MHz, CDCl3)
d = 2.04 (s, 3 H), 7.17–7.57 (m, 9 H), 7.90 (dd, J = 8.1/11.5 Hz,
2 H). 13C-NMR (75 MHz, CDCl3) d = 20.0, 125.3, 125.6, 125.7,
126.0, 126.1, 126.6, 127.4, 127.5, 128.2, 129.8, 130.3, 132.0,
133.5, 136.8, 139.8, 140.2. Anal. Calcd for C17H14 (218.29): C,
93.54; H, 6.46. Found: C, 93.57; H, 6.44.
4¢-Methoxy-2-methylbiphenyl (Table 4, Entry 11). GC-MS
(50 ◦C, 2 min → 280 ◦C, 10 ◦C min-1 → 280 ◦C, 10 min): tR =
17.3 min; m/z 198. 1H-NMR (300 MHz, CDCl3) d = 2.31 (s, 3
H), 3.88 (s, 3 H), 6.98 (d, J = 8.8 Hz, 2 H), 7.22–7.33 (m, 6 H).
13C-NMR (75 MHz, CDCl3) d = 20.5, 55.2, 113.4, 125.7, 126.9,
129.8, 130.2, 130.2, 134.3, 135.4, 141.5, 158.5. Anal. Calcd for
C14H14O (198.26): C, 84.81; H, 7.12. Found: C, 85.12; H, 7.15.
2-Methyl-4¢-phenylbiphenyl (Table ◦4, Ent◦ry 5). m.p. = 88–
89 ◦C. GC-MS (100 ◦C, 2 min → 280 C, 10 C min-1 → 280 ◦C,
10 min): tR = 17.2 min; m/z 244. 1H-NMR (300 MHz, CDCl3)
d = 2.32 (s, 3 H), 7.33–7.52 (m, 9 H), 7.56–7.71 (m, 4 H). 13C-
NMR (75 MHz, CDCl3) d = 20.5, 125.8, 126.7, 127.0, 127.2,
127.3, 128.8, 129.6, 129.8, 130.4, 135.3, 139.6, 140.8, 140.9,
141.4. Anal. Calcd for C19H16 (244.33): C, 93.40; H, 6.60. Found:
C, 93.31; H, 6.58.
4¢-Methoxybiphenyl-2-ca◦rbonitrile (Table 4, Entry 12). GC-
MS (100 ◦C, 2 min → 280 C, 10 ◦C min-1 → 280 ◦C, 10 min):
tR = 20.3 min; m/z 209. 1H-NMR (300 MHz, CDCl3) d = 3.88
(s, 3 H), 7.03 (d, J = 8.8 Hz, 2 H), 7.25–7.28 (m, 1 H), 7.41 (t,
J = 7.6 Hz, 1 H), 7.47–7.56 (m, 2 H), 7.63 (t, J = 7.7 Hz, 1
H), 7.75 (d, J = 7.7 Hz, 1 H). 13C-NMR (75 MHz, CDCl3) d =
55.3, 111.0, 114.1, 118.9, 127.0, 129.8, 129.9, 130.5, 132.7, 133.7,
145.1, 160.0. Anal. Calcd for C14H11NO (209.24): C, 80.36; H,
5.30; N, 6.69. Found: C, 80.27; H, 5.28; N, 6.71.
4¢-Methylbiphenyl-2-carbonitrile (Table 4, Entry◦6). m.p. =
49–51 ◦C. GC-MS (50 ◦C, 2 min → 280 ◦C, 10 C min-1
578 | Green Chem., 2009, 11, 574–579
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