He et al.
5
7.37 (dd, J=17.9, 7.4Hz, 6H), 7.32–7.24 (m, 3H), 7.18–7.10
9-(3′-fluoro-[1,1′-biphenyl)-4-yl)-9H-fluorene
(3l).
(m, 3H), 5.09 (s, 1H), 2.39 (s, 3H); 13C NMR (101MHz, Yield: 73%; white solid; m.p.=189.7–190.2°C; H NMR
CDCl3): δ 147.86, 141.05, 140.91, 140.58, 139.91, 138.28, (400MHz, CDCl3): δ 7.81 (d, J=7.6Hz, 2H), 7.46 (d,
128.68, 128.64, 127.91, 127.86, 127.47, 127.37, 125.38, J=8.3Hz, 2H), 7.39 (t, J=7.4Hz, 2H), 7.38–7.30 (m, 4H),
124.14, 119.92, 54.12, 21.57. HRMS (ESI): m/z [M+Na]+ 7.27 (d, J=7.4Hz, 2H), 7.24 (d, J =12Hz, 1H), 7.15 (d,
1
calcd for C26H20Na: 355.1457; found: 355.1455.
J=8.2Hz, 2H), 7.00 (td, J=8.4, 2.6Hz, 1H), 5.08 (s, 1H);
9-(3′-methoxy-[1,1′-biphenyl)-4-yl)-9H-fluorene (3g). 13C NMR (101MHz, CDCl3): δ 147.71, 143.21, 141.46,
1
Yield: 80%; white solid; m.p.=187.1–188.2°C; H NMR 141.07, 138.50, 138.47, 130.24, 130.15, 128.87, 127.46,
(400MHz, CDCl3): δ 7.81 (d, J=7.6Hz, 2H), 7.48 (d, 127.41, 125.35, 122.63, 122.60, 119.98, 114.06, 113.96,
J=8.3Hz, 2H), 7.39 (t, J=7.5Hz, 2H), 7.37–7.30 (m, 3H), 113.85, 113.75, 54.08. HRMS (ESI): m/z [M+Na]+ calcd
7.28 (t, J=6.4Hz, 2H), 7.14 (dd, J=7.4, 5.3Hz, 3H), 7.09 for C25H17F Na: 359.1206; found: 359.1209.
(s, 1H), 6.87 (d, J=8.2Hz, 2H), 5.09 (s, 1H), 3.84 (s, 3H);
9-(2′,4′-difluoro-(1,1′-biphenyl) (3m). Yield: 72%; white
13C NMR (101MHz, CDCl3): δ 159.90, 147.80, 142.44, solid; m.p.=138.4–139.1°C; 1H NMR (400MHz, CDCl3):
141.04, 140.89, 139.64, 129.72, 128.70, 127.49, 127.39, δ 7.81 (d, J=7.6Hz, 2H), 7.43–7.35 (m, 4H), 7.35 (d,
127.37, 125.37, 119.93, 119.56, 112.75, 112.58, 55.29, J=6.6Hz, 3H), 7.27 (t, J=7.4Hz, 2H), 7.15 (d, J=8.2Hz,
54.10. HRMS (ESI): m/z [M+H]+ calcd for C26H21O: 2H), 6.94–6.85 (m, 2H), 5.09 (s, 1H); 13C NMR (101MHz,
349.1593; found: 349.1587.
CDCl3): δ 163.43 (d, J=11.8Hz), 160.97 (dd, J=11.8,
9-(3′-chloro-[1,1′-biphenyl)-4-yl)-9H-fluorene
(3h). 2.8Hz), 158.49 (d, J=11.8Hz), 147.68, 141.27, 141.07,
1
Yield: 75%; white solid; m.p.=156.1–158.7°C; H NMR 133.50, 131.34 (dd, J=9.4, 5.0Hz), 129.22 (d, J=2.9Hz),
(400MHz, CDCl3): δ 7.82 (d, J=7.6Hz, 2H), 7.53 (s, 1H), 128.51, 127.42 (d, J=5.9Hz), 125.39, 119.97, 111.65 (d,
7.45 (d, J=8.3Hz, 2H), 7.43–7.37 (m, 3H), 7.33 (t, J=3.8Hz), 111.44 (d, J=3.8Hz), 104.37 (dd, J=26.9,
J=7.9Hz, 3H), 7.27 (q, J=7.0Hz, 3H), 7.16 (d, J=8.3Hz, 25.1Hz), 54.12. HRMS (ESI): m/z [M+Na]+ calcd for
2H), 5.09 (s, 1H); 13C NMR (101MHz, CDCl3): δ 147.69, C25H16F2Na: 377.1112; found: 377.1119.
142.74, 141.48, 141.05, 138.36, 134.62, 129.96, 128.87,
9-(3′,4,′5′-trifluoro-(1,1′-biphenyl) (3n). Yield: 78%;
1
127.45, 127.42, 127.40, 127.17, 127.15, 125.33, 125.15, white solid; m.p.=132.8–132.9°C; H NMR (400MHz,
119.97, 54.07. HRMS (ESI): m/z [M+Na]+ calcd for CDCl3): δ 7.81 (d, J=7.6Hz, 2H), 7.44–7.34 (m, 4H), 7.32
C25H17ClNa: 375.0911; found: 375.0916.
(d, J=6.5Hz, 2H), 7.28 (q, J=8.3Hz, 2H), 7.14 (dd,
(3i). J=14.5, 7.4Hz, 4H), 5.08 (s, 1H); 13C NMR (101MHz,
9-(2′-methyl-[1,1′-biphenyl)-4-yl)-9H-fluorene
1
Yield: 82%; white solid; m.p.=138.8–139.0°C; H NMR CDCl3): δ 152.65 (dd, J=10.0, 4.2Hz), 150.15 (d,
(400MHz, CDCl3): δ 7.83 (d, J=8.0Hz, 2H), 7.45–7.37 J=10.0Hz), 147.52, 142.19, 141.07, 140.42, 137.92,
(m, 4H), 7.30 (d, J=14.8Hz, 2H), 7.26–7.21 (m, 6H), 7.14 137.03 (d, J=4.6Hz), 136.76, 129.05, 127.49 (d,
(d, J=8.1Hz, 2H), 5.12 (s, 1H), 2.27 (s, 3H); 13C NMR J=10.0Hz), 127.18, 125.28, 120.03, 110.87 (d, J=21.8Hz),
(101MHz, CDCl3): δ 147.83, 141.65, 141.05, 140.41, 54.00. HRMS (ESI): m/z [M+Na]+ calcd for C25H15F3Na:
140.00, 135.39, 130.30, 129.82, 129.50, 127.96, 127.35, 395.1018; found: 395.1014.
127.31, 127.15, 125.72, 125.42, 119.91, 54.16, 20.54.
HRMS (ESI): m/z [M+Na]+ calcd for C26H20Na: 355.1457; solid; m.p.=188.5–191.5°C; 1H NMR (400MHz, CDCl3):
found: 355.1459. δ 7.82 (d, J=7.6Hz, 2H), 7.44 (dd, J=8.3, 1.7Hz, 2H),
9-(2′,3′-difluoro-(1,1′-biphenyl) (3o). Yield: 55%; white
9-(4-(naphthalen-2-yl)phenyl)-9H-fluorene (3j). Yield: 7.40 (t, J=7.5Hz, 2H), 7.36 (d, J=6.7Hz, 2H), 7.28 (t,
69%; white solid; m.p.=216.1–218.7°C; 1H NMR J=7.5Hz, 2H), 7.18 (d, J=8.2Hz, 2H), 7.15–7.08 (m, 3H),
(400MHz, CDCl3): δ 7.99 (s, 1H), 7.90–7.84 (t, J=8.0Hz, 5.11 (s, 1H); 13C NMR (101MHz, CDCl3): δ 147.60,
3H), 7.82 (d, J=7.4Hz, 2H), 7.70 (d, J=8.6Hz, 1H), 7.61 141.77, 141.06, 133.25, 131.00 (d, J=10.3Hz), 129.27 (d,
(d, J=8.3Hz, 2H), 7.46 (ddd, J=6.8, 4.4, 1.7Hz, 2H), 7.38 J=3.0Hz), 128.55, 127.43 (d, J=6.8Hz), 125.38, 125.21
(dd, J=13.3, 7.0Hz, 4H), 7.27 (t, J=8.0Hz, 2H), 7.19 (d, (d, J=2.4Hz), 124.02 (dd, J=7.2, 4.9Hz), 119.96, 115.93
J=8.2Hz, 2H), 5.11 (s, 1H); 13C NMR (101MHz, CDCl3): (d, J=17.5Hz), 54.12; HRMS (ESI): m/z [M+Na]+ calcd
δ 147.85, 141.09, 140.87, 139.67, 138.24, 133.70, 132.60, for C25H16F2Na: 377.1112; found: 377.1109.
128.87, 128.42, 128.20, 127.74, 127.66, 127.43, 127.41,
9-(4′-(trifluoromethyl)-[1,1′-biphenyl]-4-yl)-9H-
126.29, 125.90, 125.63, 125.51, 125.41, 119.98, 54.15. fluorene (3p). Yield: 53%; white solid; m.p.=238.7–
HRMS (ESI): m/z [M+Na]+ calcd for C29H20Na: 391.1457; 239.2°C; 1H NMR (400MHz, CDCl3): δ 7.82 (d, J=7.6Hz,
found: 391.1458.
2H), 7.64 (d, J=2.5Hz, 4H), 7.48 (d, J=8.3Hz, 2H), 7.39
9-(4′-fluoro-[1,1′-biphenyl)-4-yl)-9H-fluorene
(3k). (t, J=7.1Hz, 2H), 7.34 (d, J=7.2Hz, 2H), 7.27 (t, J=7.4Hz,
Yield: 78%; white solid; m.p.=187.1–188.2°C; H NMR 2H), 7.18 (d, J=8.2Hz, 2H), 5.10 (s, 1H); 13C NMR
(400MHz, CDCl3): δ 7.82 (d, J=7.6Hz, 2H), 7.50 (dd, (101MHz, CDCl3): δ 147.63, 144.39, 141.90, 141.08,
J=8.8, 5.3Hz, 2H), 7.43 (d, J=8.2Hz, 2H), 7.39 (t, 138.29, 128.96, 127.60, 127.50, 127.43, 127.25, 125.76,
J=7.5Hz, 2H), 7.35 (d, J=7.2Hz, 2H), 7.28 (d, J=7.5Hz, 125.72, 125.68, 125.64, 125.33, 120.01, 54.07; HRMS
2H), 7.15 (d, J=8.2Hz, 2H), 7.09 (t, J=8.7Hz, 2H), 5.09 (ESI): m/z [M+Na]+ calcd for C26H17F3Na: 409.1175;
(s, 1H); 13C NMR (101MHz, CDCl3): δ 163.61, 161.17, found: 409.1177.
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147.77, 141.04, 140.76, 138.79, 137.01, 128.79, 128.57,
9-(4′-vinyl-[1,1′-biphenyl)-4-yl)-9H-fluorene
(3q).
1
128.49, 127.41, 127.37, 127.30, 125.33, 119.95, 115.69, Yield: 48%; white solid; m.p.=221.9–222.3°C; H NMR
115.48, 54.05. HRMS (ESI): m/z [M+H]+ calcd for (400MHz, CDCl3): δ 7.82 (d, J=7.6Hz, 2H), 7.56–7.50
C25H18F: 337.1387; found: 337.1389
(m, 3H), 7.48 (d, J=8.2Hz, 3H), 7.39 (t, J=7.5Hz, 2H),