K. Fuchibe et al. / Journal of Fluorine Chemistry 179 (2015) 106–115
113
J = 1 Hz), 127.4, 127.7, 128.2 (d, J = 1 Hz), 128.41, 128.44, 129.95 (d,
J = 6 Hz), 130.01, 131.9 (d, J = 6 Hz), 140.6 (d, J = 6 Hz), 140.7, 157.2
1412, 1263, 1117, 1055, 849, 742 cmꢁ1; HRMS (EI): Calcd. for
14H8BrF [M]+: 273.9793; Found: 273.9788.
C
(d, J = 251 Hz); 19F NMR (470 MHz, CDCl3):
d
38.0 (d, J = 13 Hz); IR
˜ 3076, 1637, 1410, 1057, 748 cmꢁ1; HRMS (EI): Calcd. for
20H13F [M]+: 272.1001; Found: 272.0992.
(neat):
C
n
4.4.23. 1-Chloro-9-fluorophenanthrene 3j
1H NMR (500 MHz, CDCl3):
7.51 (dd, J = 8.0, 8.0 Hz, 1H), 7.65–
d
7.78 (m, 3H), 7.87 (d, J = 13.0 Hz, 1H), 8.21 (d, J = 7.6 Hz, 1H), 8.55
(d, J = 8.3 Hz, 1H), 8.65 (d, J = 8.0 Hz, 1H); 13C NMR (126 MHz,
CDCl3): d 104.5 (d, J = 24 Hz), 121.4 (d, J = 6 Hz), 121.6, 123.1 (d,
4.4.18. 9-Fluoro-7-methyl-1-(4-methylphenyl)phenanthrene 3e
1H NMR (500 MHz, CDCl3):
2.47 (s, 3H), 2.60 (s, 3H), 7.33 (d,
d
J = 7.9 Hz, 2H), 7.38 (ddd, J = 7.9, 1.8, 1.8 Hz, 2H), 7.46 (d,
J = 13.4 Hz, 1H), 7.51 (d, J = 7.1 Hz, 1H), 7.57 (dd, J = 8.6, 1.7 Hz,
1H), 7.62 (dd, J = 8.2, 7.1 Hz, 1H), 7.95 (s, 1H), 8.63 (d, J = 8.5 Hz,
J = 3 Hz), 124.2 (d, J = 19 Hz), 125.6 (d, J = 2 Hz), 127.5, 127.6, 128.2,
129.3, 129.5 (d, J = 10 Hz), 131.6 (d, J = 6 Hz), 131.9 (d, J = 6 Hz),
158.0 (d, J = 253 Hz); 19F NMR (470 MHz, CDCl3):
d 41.2 (d,
2H); 13C NMR (126 MHz, CDCl3):
d
21.2, 21.7, 106.1 (d, J = 22 Hz),
J = 13 Hz); IR (neat): n ;
˜ 1601, 1448, 1414, 1124, 849, 756 cmꢁ1
120.6 (d, J = 6 Hz), 121.7, 123.0 (d, J = 3 Hz), 124.0 (d, J = 19 Hz),
125.1 (d, J = 2 Hz), 128.0, 128.2, 129.1, 129.5, 129.6 (d, J = 10 Hz),
129.8, 129.9, 137.0, 137.1, 137.8, 140.5 (d, J = 6 Hz), 157.0 (d,
HRMS (EI): Calcd. for C14H8ClF [M]+: 230.0299; Found: 230.0293.
4.4.24. 1-Phenyl-7-methoxy-9-fluorophenanthrene 3k and 1-(4-
methoxyphenyl)-9-fluorophenanthrene 3k0 (58:42 mixture)
J = 250 Hz); 19F NMR (470 MHz, CDCl3):
(neat):
22H17F [M]+: 300.1314; Found: 300.1304.
d
37.2 (d, J = 13 Hz); IR
n
˜ 2922, 1618, 1458, 1209, 795 cmꢁ1; HRMS (EI): Calcd. for
1H NMR (500 MHz, CDCl3):
d 3.91 (s, 3H*0.42), 3.99 (s, 3H*0.58),
C
7.06 (ddd, J = 8.7, 2.5, 2.5 Hz, 2H*0.42), 7.36 (dd, J = 9.2, 2.7 Hz,
1H*0.58), 7.42 (ddd, J = 8.7, 2.5, 2.5 Hz, 2H*0.42), 7.44–7.56 (m,
8H*0.58 + 2H*0.42), 7.63 (dd, J = 8.2, 6.9 Hz, 1H*0.58), 7.64 (dd,
J = 6.8, 6.8 Hz, 1H*0.42), 7.69 (ddd, J = 8.2, 6.9, 1.2 Hz, 1H*0.42),
7.75 (ddd, J = 8.4, 7.0, 1.3 Hz, 1H*0.42), 8.18 (d, J = 8.0 Hz, 1H*0.42),
8.58 (d, J = 8.3 Hz, 1H*0.58), 8.64 (dd, J = 9.2, 1.7 Hz, 1H*0.58), 8.66
(d, J = 8.9 Hz, 1H*0.42), 8,75 (d, J = 8.5 Hz, 1H*0.42); 13C NMR
4.4.19. 9-Fluoro-7-methoxy-1-(4-methoxyphenyl)phenanthrene 3f
1H NMR (500 MHz, CDCl3):
3.90 (s, 3H), 3.98 (s, 3H), 7.05 (ddd,
d
J = 8.5, 2.5, 2.5 Hz, 2H), 7.34 (dd, J = 9.2, 2.7 Hz, 1H), 7.41 (ddd,
J = 8.5, 2.5, 2.5 Hz, 2H), 7.45–7.52 (m, 3H), 7.60 (dd, J = 8.3, 7.4 Hz,
1H), 8.54 (d, J = 8.3 Hz, 1H), 8.62 (dd, J = 9.2, 1.8 Hz, 1H); 13C NMR
(126 MHz, CDCl3):
d
55.4, 55.5, 101.0 (d, J = 7 Hz), 106.7 (d,
(126 MHz, CDCl3): d 55.4, 55.5, 101.0 (d, J = 7 Hz), 106.1 (d,
J = 22 Hz), 113.9, 118.6, 121.3, 124.9 (d, J = 3 Hz), 125.16 (d,
J = 19 Hz), 125.24 (d, J = 2 Hz), 126.3 (d, J = 6 Hz), 127.4, 128.3,
129.0 (d, J = 9 Hz), 131.0, 133.1, 140.2 (d, J = 6 Hz), 156.8 (d,
J = 22 Hz), 106.6 (d, J = 22 Hz), 113.9, 118.6, 121.2 (d, J = 6 Hz),
121.6, 121.8, 123.1 (d, J = 3 Hz), 123.9 (d, J = 19 Hz), 124.9 (d,
J = 3 Hz), 125.16 (d, J = 19 Hz), 125.18 (d, J = 2 Hz), 125.24 (d,
J = 2 Hz), 126.2 (d, J = 6 Hz), 126.9, 127.37, 127.41, 127.7, 128.2
(d, J = 8 Hz), 128.40, 128.44, 128.7 (d, J = 9 Hz), 130.0, 130.1 (d,
J = 10 Hz), 131.1, 131.9 (d, J = 6 Hz), 133.0, 140.2 (d, J = 6 Hz), 140.5
(d, J = 6 Hz), 140.8, 156.8 (d, J = 250 Hz), 157.1 (d, J = 251 Hz), 158.7,
J = 249 Hz), 158.7, 159.0; 19F NMR (470 MHz, CDCl3):
d 37.4 (d,
J = 13 Hz); IR (neat): n
˜ 2929, 1612, 1514, 1223, 771 cmꢁ1; HRMS
(EI): Calcd. for C22H17FO2 [M]+: 332.1213; Found: 332.1205.
4.4.20. 7-Chloro-1-(4-chlorophenyl)-9-fluorophenanthrene 3g
159.0; 19F NMR (470 MHz, CDCl3):
37.8 (d, J = 13 Hz, 1F*0.58); IR (neat): n
d
37.7 (d, J = 13 Hz, 1F*0.42),
˜ 3055, 3020, 2956, 2833,
1H NMR (500 MHz, CDCl3):
d
7.40 (ddd, J = 8.6, 2.2, 2.2 Hz, 2H),
7.42 (d, J = 12.1 Hz, 1H), 7.50 (ddd, J = 8.6, 2.2, 2.2 Hz, 2H), 7.52 (d,
J = 7.1 Hz, 1H), 7.66 (dd, J = 8.3, 7.1 Hz, 1H), 7.68 (dd, J = 8.9, 2.2 Hz,
1H) 8.13 (d, J = 2.2 Hz, 1H), 8.61 (d, J = 8.3 Hz, 1H), 8.64 (dd, J = 8.9,
1614, 1456, 1240, 1223, 768 cmꢁ1; HRMS (EI): Calcd. for C21H15FO
[M]+: 302.1107; Found (major isomer on GC–MS analysis):
302.1118; Found (minor isomer on GC–MS analysis): 302.1116.
1.8 Hz, 1H); 13C NMR (126 MHz, CDCl3):
d 107.0 (d, J = 21 Hz),
120.7 (d, J = 7 Hz), 122.3, 124.8 (d, J = 3 Hz), 124.9 (d, J = 19 Hz),
125.6 (d, J = 2 Hz), 127.8 (d, J = 1 Hz), 128.4, 128.6, 128.7, 129.6 (d,
J = 9 Hz), 130.1 (d, J = 5 Hz), 131.2, 133.4, 133.7, 138.8, 139.4 (d,
4.4.25. 7-Chloro-9-fluoro-1-phenylphenanthrene 3l and 1-(4-
chlorophenyl)-9-fluorophenanthrene 3l0 (88:12 mixture)
1H NMR (500 MHz, CDCl3):
(ddd, J = 8.5, 2.0, 2.0 Hz,
d
7.37 (d, J = 12.7 Hz, 1H*0.12), 7.40
2H*0.12), 7.43–7.53 (m,
J = 6 Hz), 156.2 (d, J = 252 Hz); 19F NMR (470 MHz, CDCl3):
d
38.6
(d, J = 12 Hz); IR (neat):
n
˜ 3080, 1603, 1481, 1456, 1097, 793,
6H*0.88 + 3H*0.12), 7.54 (d, J = 7.1 Hz, 1H*0.88), 7.60–7.66 (m,
2H*0.88 + 1H*0.12), 7.67 (ddd, J = 8.1, 7.1, 1.0 Hz, 1H*0.12), 7.73
(ddd, J = 8.3, 7.0, 1.3 Hz, 1H*0.12), 8.10 (d, J = 2.2 Hz, 1H*0.88), 8.16
(dd, J = 8.0, 1.5 Hz, 1H*0.12), 8.56 (d, J = 8.4 Hz, 1H*0.88), 8.60 (dd,
J = 9.0, 1.8 Hz, 1H*0.88), 8.65 (d, J = 8.4 Hz, 1H*0.12), 8.71 (d,
748 cmꢁ1; HRMS (EI): Calcd. for C20H11Cl2F [M]+: 340.0222;
Found: 340.0219.
4.4.21. 9-Fluoro-1-iodophenanthrene 3h
1H NMR (500 MHz, CDCl3):
d
7.31 (dd, J = 8.0, 8.0 Hz, 1H), 7.72
J = 8.3 Hz, 1H*0.12); 13C NMR (126 MHz, CDCl3):
d 105.7 (d,
(ddd, J = 7.0, 7.0, 1.0 Hz, 1H), 7.76 (ddd, J = 8.4, 8.4, 1.7 Hz, 1H), 7.81
(d, J = 12.9 Hz, 1H), 8.18 (d, J = 7.5 Hz, 1H), 8.22 (dd, J = 7.9, 1.2 Hz,
J = 22 Hz), 107.4 (d, J = 21 Hz), 120.6 (d, J = 7 Hz), 121.2 (d, J = 6 Hz),
122.0, 122.4, 123.0 (d, J = 3 Hz), 123.9 (d, J = 19 Hz), 124.8 (d,
J = 3 Hz), 124.9 (d, J = 20 Hz), 125.2 (d, J = 2 Hz), 125.6 (d, J = 2 Hz),
127.1, 127.6, 127.7, 127.9, 128.2 (d, J = 11 Hz), 128.2, 128.3, 128.5,
128.7, 129.7 (d, J = 10 Hz), 129.8 (d, J = 9 Hz), 129.9, 130.1 (d,
J = 6 Hz), 131.3, 131.8 (d, J = 6 Hz), 133.2, 133.6, 139.1, 139.2
(d, J = 6 Hz), 140.3, 140.8 (d, J = 6 Hz), 156.0 (d, J = 251 Hz), 157.3 (d,
1H), 8.64–8.69 (m, 2H); 13C NMR (126 MHz, CDCl3):
d 99.2 (d,
J = 6 Hz), 112.5 (d, J = 24 Hz), 121.4 (d, J = 6 Hz), 122.9 (d, J = 3 Hz),
123.3 (d, J = 1 Hz), 124.2 (d, J = 19 Hz), 126.7 (d, J = 2 Hz), 127.6,
128.2, 128.8, 131.8 (d, J = 6 Hz), 133.5 (d, J = 11 Hz), 138.6, 158.5 (d,
J = 253 Hz); 19F NMR (470 MHz, CDCl3):
(neat):
14H8FI [M]+: 321.9655; Found: 321.9641.
d
41.5 (d, J = 13 Hz); IR
n
˜ 1637, 1410, 1265, 1055, 748 cmꢁ1; HRMS (EI): Calcd. for
J = 251 Hz); 19F NMR (470 MHz, CDCl3):
1F*0.88), 38.5 (d, J = 13 Hz, 1F*0.12); IR (neat):
d
38.0 (d, J = 13 Hz,
n
˜ 3060, 3024, 1601,
C
1456, 1217, 771 cmꢁ1; HRMS (EI): Calcd. for C20H12ClF [M]+:
306.0612; Found (major isomer on GC–MS analysis): 306.0620;
Found (minor isomer on GC–MS analysis): 306.0599.
4.4.22. 1-Bromo-9-fluorophenanthrene 3i
1H NMR (500 MHz, CDCl3):
7.46 (dd, J = 8.0, 8.0 Hz, 1H), 7.71–
d
7.79 (m, 2H), 7.89 (d, J = 7.4 Hz, 1H), 7.90 (d, J = 13.0 Hz, 1H), 8.22
(d, J = 8.0 Hz, 1H), 8.63 (d, J = 8.3 Hz, 1H), 8.68 (d, J = 8.2 Hz, 1H);
4.4.26. 9-Butyl-10-fluorophenanthrene 3m
13C NMR (126 MHz, CDCl3):
d
107.2 (d, J = 24 Hz), 121.4 (d,
1H NMR (500 MHz, CDCl3):
d 0.98 (t, J = 7.2 Hz, 3H), 1.46–1.55
J = 4 Hz), 122.2, 122.7 (d, J = 3 Hz), 123.0, 124.1 (d, J = 20 Hz), 126.0,
127.5, 128.1, 129.3, 130.8, 131.2, 131.6, 158.1 (d, J = 253 Hz); 19F
(m, 2H), 1.69–1.77 (m, 2H), 3.13–3.20 (m, 2H), 7.58–7.70 (m, 4H),
8.06 (d, J = 7.0 Hz, 1H), 8.17 (d, J = 7.0 Hz, 1H), 8.64–8.71 (m, 2H);
13C NMR (126 MHz, CDCl3):
d 14.0, 22.8, 24.3 (d, J = 5 Hz), 32.0,
NMR (470 MHz, CDCl3):
d
41.3 (d, J = 13 Hz); IR (neat):
n˜ 1442,