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7.54 (t, J=7.1 Hz, 6H), 7.15 (dd, J=
19.0, 6.0 Hz, 4H), 6.98–6.77 (m,
4H), 3.90 (s, 3H), 3.82 (s, 3H), 2.45
(s, 3H), 2.34 ppm (s, 3H); 13C NMR
(100 MHz,
CDCl3):
d=165.62,
165.45, 162.67, 162.01, 150.99,
150.70, 148.77, 147.28, 142.33,
141.93, 141.03, 138.18, 133.56,
133.47, 130.39, 130.35, 129.65,
129.54, 128.57, 127.36, 124.77,
123.81, 122.71, 118.99, 117.62,
114.08, 112.84, 108.19, 55.82, 55.51,
21.46, 21.38 ppm; IR (KBr): n˜ =
3687, 3541, 2913, 1815, 1584,
1435, 1128, 754, 579, 526 cmÀ1; MS
(EI, 70 eV) m/z: 302.09 (M+).
(E)-1-(5-Methoxy-[1,1’-biphenyl]-
2-yl)-2-phenyldiazene
(3ja):
Yellow oil; 44.4 mg, 77% yield;
1H NMR (400 MHz, CDCl3): d=8.23
(t, J=10.4 Hz, 1H), 7.92 (d, J=
Scheme 4. Proposed catalytic cycle.
8.7 Hz, 2H), 7.88 (d, J=7.5 Hz, 2H),
7.51 (dd, J=13.8, 6.9 Hz, 3H), 7.42
(d, J=7.2 Hz, 2H), 7.24–7.17 (m,
1H), 7.02 (d, J=8.7 Hz, 2H), 3.89 ppm (s, 3H); 13C NMR (100 MHz,
CDCl3): d=162.0, 147.0, 130.3, 129.0, 124.7, 122.5, 114.2, 55.5 ppm;
IR (KBr): n˜ =3433, 2838, 2360, 1741, 1255, 1028, 837, 806, 751,
548 cmÀ1; MS (EI, 70 eV) m/z: 288.01 (M+).
165.3, 163.0, 162.8, 149.3, 145.9, 143.7, 143.6, 137.8, 130.7, 128.7,
128.6, 127.8, 127.7, 125.2, 125.1, 118.0, 117.9, 117.3, 117.0, 116.1,
115.9, 115.3, 115.0 ppm; IR (KBr): n˜ =3673, 3446, 2649, 1081, 893,
765, 700, 578, 524 cmÀ1; MS (EI, 70 eV) m/z: 294.00 (M+).
(E)-1-(5-Chloro-[1,1’-biphenyl]-2-yl)-2-(4-chlorophenyl)diazene
(3 fa): Yellow solid; 36 mg, 58% yield; m.p.: 89–918C; 1H NMR
(400 MHz, CDCl3): d=7.85 (t, J=7.7 Hz, 1H), 7.72 (dd, J=13.7,
8.7 Hz, 2H), 7.58 (d, J=2.2 Hz, 1H), 7.51–7.39 ppm (m, 8H);
13C NMR (100 MHz, CDCl3): d=151.0, 150.8, 147.7, 142.9, 137.4,
137.1, 136.9, 130.7, 129.4, 129.3, 128.2, 127.8, 124.5, 124.2,
117.3 ppm; IR (KBr): n˜ =3694, 3472, 2921, 1383, 960, 883, 656, 572,
482 cmÀ1; MS (EI, 70 eV) m/z: 325.96 (M+).
(E)-1-(4’-Methyl-[1,1’-biphenyl]-2-yl)-2-phenyldiazene
(3ab):
1
Yellow oil; 43 mg, 79% yield; H NMR (400 MHz, CDCl3): d=7.80 (d,
J=7.4 Hz, 2H), 7.73 (d, J=8.0 Hz, 1H), 7.58 (d, J=7.6 Hz, 1H), 7.52
(dd, J=13.6, 5.9 Hz, 1H), 7.49–7.40 (m, 5H), 7.37 (d, J=7.9 Hz, 2H),
7.22 (d, J=7.4 Hz, 1H), 2.43 ppm (s, 3H); 13C NMR (100 MHz,
CDCl3): d=152.9, 149.8, 141.0, 137.0, 135.8, 130.8, 130.7, 129.1,
129.0, 128.8, 128.4, 128.3, 127.8, 127.5, 123.2, 120.4, 115.9,
˜
21.2 ppm; IR (KBr): n=3738, 2921, 1785, 1450, 1410, 961, 926,
513 cmÀ1; MS (EI, 70 eV) m/z: 272.06 (M+).
(E)-1-(5-Bromo-[1,1’-biphenyl]-2-yl)-2-(4-bromophenyl)diazene
(3ga): Yellow solid; 35 mg, 42% yield; m.p.: 133–1378C; 1H NMR
(400 MHz, CDCl3): d=7.71–7.66 (m, 1H), 7.58 (dd, J=20.6, 12.0 Hz,
4H), 7.53–7.49 (m, 2H), 7.37 ppm (d, J=8.8 Hz, 5H); 13C NMR
(100 MHz, CDCl3): d=151.4, 148.1, 143.1, 137.3, 133.7, 132.4, 131.1,
130.7, 127.8, 127.8, 124.7, 124.4, 117.5 ppm; IR (KBr): n˜ =3682,
2840, 1725, 1493, 1147, 749, 688, 484 cmÀ1; MS (EI, 70 eV) m/z:
413.81 (M+).
(E)-1-(4’-Methoxy-[1,1’-biphenyl]-2-yl)-2-phenyldiazene
(3ad):
1
Yellow oil; 49 mg, 85% yield; H NMR (400 MHz, CDCl3): d=7.97–
7.89 (m, 1H), 7.86–7.78 (m, 2H), 7.73 (d, J=8.0 Hz, 1H), 7.58 (dd,
J=7.6, 1.4 Hz, 1H), 7.56–7.50 (m, 2H), 7.46 (dd, J=15.3, 7.4 Hz,
4H), 7.37 (d, J=8.0 Hz, 2H), 2.43 ppm (s, 3H); 13C NMR (100 MHz,
CDCl3): d=152.90, 149.80, 141.03, 137.03, 135.87, 130.82, 130.78,
129.13, 129.05, 128.43, 127.80, 123.26, 115.96, 21.21 ppm; IR (KBr):
n˜ =3798, 2821, 1685, 1459, 1420, 921, 513 cmÀ1; MS (EI, 70 eV) m/z:
288.16 (M+).
(E)-Ethyl-6-((4-(ethoxycarbonyl)phenyl)diazenyl)-[1,1’-biphenyl]-
3-carboxylate (3ha): Yellow solid; 38.6 mg, 48% yield; m.p.: 118–
119 8C; 1H NMR (400 MHz, CDCl3): d=8.30 (d, J=1.6 Hz, 1H), 8.13
(dd, J=13.8, 5.2 Hz, 3H), 7.83 (d, J=8.5 Hz, 2H), 7.77 (d, J=8.4 Hz,
1H), 7.51–7.42 (m, 5H), 4.42 (dd, J=14.4, 7.1 Hz, 4H), 1.42 ppm (dt,
J=9.5, 7.1 Hz, 6H); 13C NMR (100 MHz, CDCl3): d=165.9, 155.0,
152.0, 141.3, 137.8, 132.6, 132.3, 130.8, 130.6, 129.2, 127.8, 123.1,
116.0, 61.4, 61.3, 14.3, 14.3 ppm; IR (KBr): n˜ =3125, 2989, 1735,
1634, 1468, 1246, 1106, 1056, 846, 526 cmÀ1; MS (EI, 70 eV) m/z:
402.09 (M+).
(E)-1-(4’-Chloro-[1,1’-biphenyl]-2-yl)-2-phenyldiazene
(3ae):
1
Yellow oil; 31.6 mg, 54% yield; H NMR (400 MHz, CDCl3): d=7.87
(d, J=7.1 Hz, 1H), 7.77 (t, J=7.3 Hz, 3H), 7.54 (d, J=3.7 Hz, 2H),
7.47 (dd, J=13.1, 6.1 Hz, 4H), 7.40 ppm (s, 3H); 13C NMR (100 MHz,
CDCl3): d=152.8, 149.5, 140.0, 137.3, 133.5, 133.2, 133.2, 132.1,
131.1, 130.9, 130.6, 129.3, 129.1, 128.4, 127.8, 123.2, 122.2, 120.4,
119.9, 118.2, 116.0 ppm; IR (KBr): n˜ =3433, 2924, 2340, 1744, 1589,
1056, 749, 655, 524 cmÀ1; MS (EI, 70 eV) m/z: 292.07 (M+).
(E)-1-(5-Methoxy-[1,1’-biphenyl]-2-yl)-2-(p-tolyl) diazene (3ia)
and (E)-1-(4-methoxyphenyl)-2-(5-methyl-[1,1’-biphenyl]-2-yl)dia-
zene (3ai): Yellow solid; 43.5 mg, 72% yield; m.p.: 66–698C;
1H NMR (400 MHz, CDCl3): d=8.26 (d, J=7.6 Hz, 4H), 7.89 (d, J=
8.7 Hz, 1H), 7.77 (d, J=8.6 Hz, 1H), 7.66 (dd, J=5.7, 3.1 Hz, 4H),
(E)-1-(4’-Fluoro-[1,1’-biphenyl]-2-yl)-2-phenyldiazene (3af): Yellow
oil; 22.1 mg, 40% yield; H NMR (400 MHz, CDCl3): d=7.92 (d, J=
7.2 Hz, 1H), 7.82–7.70 (m, 2H), 7.58–7.52 (m, 3H), 7.45 (dt, J=8.5,
5.5 Hz, 5H), 7.12 ppm (t, J=8.7 Hz, 2H); 13C NMR (100 MHz, CDCl3):
d=163.6, 161.2, 152.8, 152.6, 149.6, 140.1, 132.4, 132.3, 131.3,
1
ChemCatChem 2015, 7, 4137 – 4142
4141
ꢀ 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim