T. Linker et al.
138.4 ppm (3 s, C-9, C-10, C-1 Ar, C-2 Ar); IR (KBr): n˜ =3058, 3012,
2919, 1491, 1438, 1381, 942, 768, 750 cmꢀ1; elemental analysis calcd (%)
for C28H22 (358.3): C 93.81, H 6.19; found: C 93.61, H 6.27.
C-7), 125.6, 125.7 (d, C-3 Ar, C-4 Ar), 127.1 (d, C-1, C-4, C-5, C-8), 128.3
(d, C-5 Ar), 130.1 (s, C-11, C-12, C-13, C14), 131.4 (d, C-6 Ar), 136.2,
137.2, 148.8 ppm (3 s, C-9, C-10, C-1 Ar, C-2 Ar); IR (KBr): n=3058,
2961, 2926, 2865, 1488, 1440, 1385, 1079, 1027, 944, 761, 667 cmꢀ1; ele-
mental analysis calcd (%) for C32H30 (414.3): C 92.71, H 7.29; found: C
92.66, H 7.33.
9-(2-Methylphenyl)anthracene (4a): Yield: 107 mg (14%); Rf =0.20
(hexane/ethyl acetate 50:1); m.p. 2108C; 1H NMR (300 MHz, CDCl3):
d=1.90 (s, 3H; Me), 7.27–7.29 (m, 1H), 7.33–7.43 (m, 3H), 7.45–7.48 (m,
4H), 7.50–7.56 (m, 2H), 8.07 (d, J=8.4 Hz, 2H; 4-H, 5-H), 8.52 ppm (s,
1H; 10-H); 13C NMR (75 MHz, CDCl3): d=19.7 (q, Me), 125.1, 125.8,
126.3, 126.5, 127.8, 128.4 (6 d, C-1, C-2, C-3, C-4, C-5, C-6, C-7, C-8, C-
10, C-3 Ar, C-5 Ar), 129.9 (s, C-11, C-14), 130.0, 131.2 (2 d, C-6 Ar, C-4
Ar), 131.4 (s, C-12, C-13), 136.4, 137.8, 138.1 ppm (3 s, C-9, C-1 Ar, C-2
Ar); IR (KBr): n˜ =3052, 2920, 2855, 1489, 1440, 1380, 1354, 1011, 934,
886, 847, 754, 738, 639, 611 cmꢀ1; MS (MALDI-TOF): m/z (%): 269 (2)
[M+H]+, 268 (2) [M]+; elemental analysis calcd (%) for C21H16 (268.3):
C 94.02, H 5.97; found: C 93.87, H 6.09.
9-(2-Isopropylphenyl)anthracene (4c): Yield: 217 mg (25%); Rf =0.33
(hexane/ethyl acetate 10:1); m.p. 1508C; 1H NMR (300 MHz, CDCl3):
d=0.98 (d, J=6.8 Hz, 6H; Me), 2.51 (sept., J=6.8 Hz, 1H; CH), 7.21 (d,
J=7.5 Hz, 1H), 7.31–7.39 (m, 3H), 7.46 (t, J=6.6 Hz, 2H), 7.52–7.60 (m,
4H), 8.06 (d, J=8.5 Hz, 2H; 4-H, 5-H), 8.51 ppm (s, 1H; 10-H);
13C NMR (75 MHz, CDCl3): d=24.1 (q, Me), 30.4 (d, CH), 125.1, 125.2,
125.6, 126.3, 126.9, 128.3, 128.3 (7 d, C-1, C-2, C-3, C-4, C-5, C-6, C-7, C-
8, C-10, C-3 Ar, C-5 Ar), 130.5 (s, C-10), 131.2, 131.4 (2 d, C-4 Ar, C-6
Ar), 136.4, 136.4, 136.9, 148.6 ppm (4 s, C-9, C-12, C-13, C-1 Ar, C-2 Ar);
IR (KBr): n=3045, 2960, 2864, 1442, 1356, 1010, 937, 889, 847, 753, 734,
641, 611 cmꢀ1; MS (MALDI-TOF): m/z (%): 296 (2) [M+H]+; elemental
analysis calcd (%) for C23H20 (296.4): C 93.20, H 6.80; found: C 93.18, H
7.11.
syn-9,10-Bis(2-ethylphenyl)anthracene (syn-3b): Yield: 380 mg (34%);
Rf =0.20 (hexane/ethyl acetate 50:1); m.p. 2228C; 1H NMR (300 MHz,
CDCl3): d=0.91 (t, J=7.5 Hz, 6H; CH3), 2.25 (q, J=7.5 Hz, 4H; CH2),
7.28–7.33 (m, 6H; 2-H, 3-H, 6-H, 7-H, 3-H Ar), 7.38–7.45 (m, 2H; 4-H
Ar), 7.52–7.58 ppm (m, 7H; 1-H, 4-H, 5-H, 8-H, 5-H Ar, 6-H Ar);
13C NMR (75 MHz, CDCl3): d=14.7 (q, CH3), 26.3 (t, CH2), 124.9 (d, C-
2, C-3, C-6, C-7), 125.8 (d, C-4 Ar), 126.9 (d, C-1, C-4, C-6, C-8), 128.0,
128.2 (2 d, C-3 Ar, C-5 Ar), 129.9 (s, C-11, C-12, C-13, C-14), 131.5 (d, C-
6 Ar), 136.2, 137.2, 143.8 ppm (3 s, C-9, C-10, C-1 Ar, C-2 Ar); IR (KBr):
n˜ =3058, 2965, 2931, 2870, 1488, 1438, 1386, 942, 752, 667 cmꢀ1; MS
(MALDI-TOF): m/z (%): 387 (4) [M+H]+.
syn-9,10-Bis(2-methoxyphenyl)anthracene (syn-3d): Yield: 405 mg
(36%); Rf =0.33 (hexane/ethyl acetate 10:1); m.p. 3088C; 1H NMR
(300 MHz, CDCl3): d=3.67 (s, 6H; OMe), 7.18–7.24 (m, 4H), 7.32–7.36
(m, 4H; 2-H, 3-H, 6-H, 7-H), 7.57 (dt, J=7.4, 1.8 Hz, 2H), 7.67–7.70 ppm
13
˜
(m, 4H; 1-H, 4-H, 5-H, 8-H); C NMR (75 MHz, CDCl3): d=55.6 (q,
OMe), 111.3 (d, C-3 Ar), 120.6 (d, C-4 Ar), 124.7 (d, C-2, C-3, C-6, C-7),
126.9 (d, C-1, C-4, C-5, C-8), 127.7 (s, C-11, C-12, C-13, C-14), 129.2,
130.1 (2 d, C-5 Ar, C-6 Ar), 133.0, 133.7 (2 s, C-9, C-10, C-1 Ar),
158.1 ppm (s, C-2 Ar); IR (KBr): n˜ =3059, 2933, 2833, 1597, 1577, 1494,
anti-9,10-Bis(2-ethylphenyl)anthracene (anti-3b): Yield: 310 mg (29%);
m.p. 2978C; 1H NMR (300 MHz, CDCl3): d=0.92 (t, J=7.5 Hz, 6H;
CH3), 2.24 (q, J=7.5 Hz, 4H; CH2), 7.28–7.33 (m, 6H; 2-H, 3-H, 6-H, 7-
H, 3-H Ar), 7.38–7.45 (m, 2H; 4-H Ar), 7.52–7.58 ppm (m, 8H; 1-H, 4-
H, 5-H, 8-H, 5-H Ar, 6-H Ar); 13C NMR (75 MHz, CDCl3): d=14.9 (q,
CH3), 26.2 (t, CH2), 125.0 (d, C-2, C-3, C-6, C-7), 125.7 (d, C-4 Ar), 126.9
(d, C-1, C-4, C-5, C-8), 128.0, 128.2 (2 d, C-3 Ar, C-5 Ar), 130.0 (s, C-11,
C-12, C13, C-14), 131.5 (d, C-6 Ar), 136.2, 137.9, 143.8 ppm (3 s, C-9, C-
10, C-1 Ar, C-2 Ar); IR (KBr): n˜ =3053, 2964, 2930, 2868, 1486, 1439,
1387, 942, 771, 757, 668 cmꢀ1; elemental analysis calcd (%) for C30H26
(386.3): C 93.22, H 6.78; found: C 92.98, H 6.90.
1459, 1432, 1274, 1243, 1106, 1046, 1022, 942, 752, 665 cmꢀ1
; MS
(MALDI-TOF): m/z (%): 391 (100) [M+H]+, 390 (77) [M]+, 375 (15)
[MꢀCH3]+.
anti-9,10-Bis(2-methoxyphenyl)anthracene (anti-3d): Yield: 496 mg
(44%); m.p. 3188C; 1H NMR (300 MHz, CDCl3): d=3.66 (s, 6H; OMe),
7.18–7.24 (m, 4H), 7.32–7.36 (m, 4H; 2-H, 3-H, 6-H, 7-H), 7.57 (dt, J=
7.4, 1.8 Hz, 2H; 5-H Ar), 7.67–7.70 ppm (m, 4H; 1-H, 4-H, 5-H, 8-H);
13C NMR (75 MHz, CDCl3): d=55.6 (q, OMe), 111.3 (d, C-3 Ar), 120.6
(d, C-4 Ar), 124.7 (d, C-2, C-3, C-6, C-7), 126.9 (d, C-1, C-4, C-5, C-8),
127.7 (s, C-11, C-12, C-13, C-14), 129.2, 130.1 (2 d, C-5 Ar, C-6 Ar),
133.0, 133.7 (2 s, C-9, C-10, C-1 Ar), 158.1 ppm (s, C-2 Ar); IR (KBr):
n˜ =3024, 2931, 2834, 1596, 1576, 1491, 1459, 1431, 1291, 1277, 1240, 1104,
1046, 1019, 942, 752, 665 cmꢀ1; elemental analysis calcd (%) for C28H22O2
(390.2): C 86.13, H 5.68; found: C 85.73, H 5.51.
9-(2-Ethylphenyl)anthracene (4b): Yield: 107 mg (13%); Rf =0.20
(hexane/ethyl acetate 50:1); m.p. 1228C; 1H NMR (300 MHz, CDCl3):
d=0.91 (t, J=7.5 Hz, 3H; CH3), 2.23 (q, J=7.6 Hz, 2H; CH2), 7.26–7.29
(m, 1H), 7.34–7.39 (m, 2H), 7.41–7.44 (m, 1H), 7.46–7.51 (m, 2H), 7.53–
7.59 (m, 4H), 8.07 (d, J=8.4 Hz, 2H; 4-H, 5-H), 8.53 ppm (s, 1H; 10-H);
13C NMR (75 MHz, CDCl3): d=14.9 (q, Me), 26.3 (t, CH2), 125.1, 125.3,
125.7, 126.3, 126.7, 128.1, 128.3, 128.4 (8 d, C-1, C-2, C-3, C-4, C-5, C-6,
C-7, C-8, C-10, C-3 Ar, C-5 Ar), 130.3 (s, C-11, C-14), 131.3 (d, C-4 Ar),
131.4 (s, C-12, C-13), 136.3, 137.6, 143.7 ppm (3 s, C-9, C-1 Ar, C-2 Ar);
IR (KBr): n=3051, 2963, 2870, 1442, 1355, 1010, 936, 889, 847, 752, 734,
640, 611 cmꢀ1; MS (MALDI-TOF): m/z (%): 283 (100) [M]+; elemental
analysis calcd (%) for C22H18 (282.3): C 93.61, H 6.38; found: C 93.44, H
6.59.
syn- and anti-9,10-Bis(2-fluorophenyl)anthracene (syn- and anti-3e):
Yield: 785 mg as a mixture of the two isomers (74%) by the thermal pro-
cedure; 944 mg (90%) under microwave conditions; Rf =0.3 (hexane/
ethyl acetate 50:1); m.p. 2658C; 1H NMR (300 MHz, CDCl3): d=7.33–
7.42 (m, 4H; 2-H, 3-H, 6-H, 7-H), 7.44–7.51 (m, 2H), 7.54–7.62 (m, 2H),
7.66–7.70 ppm (m, 4H; 1-H, 4-H, 5-H, 8-H); 13C NMR (75 MHz, CDCl3):
d=115.9 (d, JC,F =22.2 Hz, C-3 Ar), 124.2 (d, JC,F =3.8 Hz, C-5 Ar), 125.5
(d, C-2, C-3, C-6, C-7), 126.1 (s, JC,F =17.5 Hz, C-1 Ar), 126.5 (d, C-1, C-
4, C-5, C-8), 129.9 (d, JC,F =7.6 Hz, C-4 Ar), 130.1 (s, C-11, C-12, C-13, C-
14), 131.1 (s, C-9, C-10), 131.2 (s, C-9, C-10), 133.4 (d, JC,F=3.5 Hz, C-6
Ar), 160.8 ppm (s, JC,F =246 Hz, C-16); 19F NMR (282.4 MHz, CDCl3 +
CFCl3)=ꢀ113.15 (m, 2F, syn-1e), ꢀ114.1 ppm (m, 2F, anti-1e); n˜ =2962,
syn-9,10-Bis(2-isopropylphenyl)anthracene (syn-3c): Yield: 408 mg
(34%); Rf =0.35 (hexane/ethyl acetate 1:50); m.p. 2638C; 1H NMR
(300 MHz, CDCl3): d=1.06 (d, J=6.8 Hz, 12H; CH3), 2.51 (sept., J=
6.8 Hz, 2H; CH), 7.24 (dd, J=7.5, 1.1 Hz, 2H; 3-H Ar), 7.29–7.32 (m,
6H; 2-H, 3-H, 6-H, 7-H, 4-H Ar), 7.38 (dt, J=7.5, 1.6 Hz, 2H; 5-H Ar),
7.56–7.61 ppm (m, 6H; 1-H, 4-H, 5-H, 8-H, 6-H Ar); 13C NMR (75 MHz,
CDCl3): d=24.2 (q, CH3), 30.5 (d, CH), 124.9 (d, C-2, C-3, C-6, C-7),
125.6 (d, C-3 Ar, C-4 Ar), 127.1 (d, C-1, C-4, C-5, C-8), 128.3 (d, C-5
Ar), 130.2 (s, C-11, C-12, C-13, C14), 131.4 (d, C-6 Ar), 136.2, 137.3,
148.6 ppm (3 s, C-9, C-10, C-1 Ar, C-2 Ar); IR (KBr): n˜ =3059, 2960,
1490, 1447, 1387, 1262, 1223, 1094, 1028, 944, 817, 756 cmꢀ1
; MS
(MALDI-TOF): m/z (%): 367 (6) [M+H]+, 366 (20) [M]+; elemental
analysis calcd (%) for C26H16F2 (366.7): C 85.29, H 4.37; found: C 85.78,
H 3.88.
syn-9,10-Bis(2-cyanophenyl)anthracene (syn-3 f): Instead of 2-cyanophe-
nylboronic acid (2 f), 2-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)benzonitrile
(3.18 g, 5 equiv, 14.7 mmol) was used. Yield: 290 mg (26%); Rf =0.31
(hexane/ethyl acetate 3:1); m.p. 3158C; 1H NMR (300 MHz, CDCl3): d=
7.40–7.46 (m, 4H; 2-H, 3-H, 6-H, 7-H), 7.50–7.56 (m, 4H; 1-H, 4-H, 5-H,
8-H), 7.59 (d, J=7.7 Hz, 2H; 6-H Ar), 7.70 (dd, J=7.6 Hz, 7.7 Hz, 2H;
4-H Ar), 7.85 (dd, J=7.6 Hz, 7.7 Hz, 2H; 5-H Ar), 7.99 ppm (d, J=
7.6 Hz, 2H; 3-H Ar); 13C NMR (75 MHz, CDCl3): d=115.8 (s, C-2 Ar),
117.5 (s, CN), 126.4 (d, C-2, C-3, C-6, C-7), 126.6 (d, C-1, C-4, C-5, C-8),
128.9 (d, C-6 Ar), 130.2 (s, C-11, C-12, C-13, C-14), 132.8 (d, C-4 Ar),
2926, 2866, 1488, 1439, 1386, 1082, 1025, 944, 771, 668 cmꢀ1
; MS
(MALDI-TOF): m/z (%): 415 (1) [M+H]+, 414 (2) [M]+.
anti-9,10-Bis(2-isopropylphenyl)anthracene (anti-3c): Yield: 346 mg
(29%); 1H NMR (300 MHz, CDCl3): d=1.01 (d, J=6.8 Hz, 12H; CH3),
2.44 (sept., J=6.9 Hz, 2H; CH), 7.17 (d, J=7.5, 2H; 3-H Ar), 7.29–7.32
(m, 6H; 2-H, 3-H, 6-H, 7-H, 4-H Ar), 7.38 (dt, J=7.5, 1.8 Hz, 2H; 5-H
Ar), 7.55–7.59 ppm (m, 6H; 1-H, 4-H, 5-H, 8-H, 6-H Ar); 13C NMR
(75 MHz, CDCl3): d=24.2 (q, CH3), 30.4 (d, CH), 124.9 (d, C-2, C-3, C-6,
11438
ꢀ 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2008, 14, 11429 – 11441