Pei et al.
Gen er a l P r oced u r e for P r ep a r a tion of 2-(5-Br om o-4-
h exylth ien yl)-9,9′-sp ir obiflu or en e (9) a n d 2-(5′-Br om o-
3,4′-dih exyl-5,2′-bith ioph en e-2-yl)-9,9′-spir obiflu oen e (13).
N-Bromosuccinimide (0.356 g, 2.05 mmol) was added slowly
in portions to a solution of compound 5a or 6a (2 mmol) in 25
mL of acetic acid and chloroform (1:1) at 0 °C. The mixture
was stirred overnight at room temperature, poured into water,
and then extracted with chloroform. The combined organic
layers were washed with saturated NaHCO3 and brine and
were dried over Na2SO4. After the solvent was removed by
rotary evaporation, the remaining solid was recrystallized from
CHCl3/EtOH to give pure products.
2-(5-Br om o-4-h exylt h ien yl)-9,9′-sp ir ob iflu or en e (9).
Brown crystals (yield 95%). EI-MS (m/z): 562, 560 (M+, 100).
1H NMR (CDCl3, 300 MHz) δ: 7.82-7.90 (4H, m, Ar-H), 7.52-
7.55 (1H, dd, J ) 1.6, 8.0 Hz, Ar-H), 7.35-7.43 (3H, m, Ar-H),
7.09-7.16 (3H, m, Ar-H), 6.89-6.90 (1H, d, J ) 1.6 Hz, Ar-
H), 6.83 (1H, s, Th-H), 6.77-6.79 (2H, d, J ) 7.6 Hz, Ar-H),
6.71-6.74 (1H, d, J ) 7.6 Hz, Ar-H), 2.45-2.50 (2H, t, J ) 7.6
Hz, CH2), 1.49-1.56 (4H, m, CH2), 1.28-1.34 (6H, m, CH2),
0.86-0.91 (3H, t, J ) 6.6 Hz, CH3). 13C NMR (CDCl3, 75.5
MHz) δ: 149.5, 149.1, 148.4, 143.5, 143.0, 141.7, 141.4, 141.0,
133.4, 127.9, 127.8, 127.7, 125.3, 124.1, 123.9, 120.7, 120.4,
120.0, 119.9, 112.0, 107.8, 31.5, 29.6, 29.5, 28.8, 22.5, 14.0. FT-
IR (λ, cm-1): 3057, 2927, 1448, 824, 754, 730, 636. Anal. Calcd
for C35H29BrS: C, 74.86; H, 5.21; S, 5.71, Br, 14.23. Found:
C, 74.87; H, 5.41; S, 5.36; Br, 14.49.
2,2′-Bis(4-h exylth ien yl)-9,9′-sp ir obiflu or en e (5c). Yel-
low crystals (yield 97%). EI-MS (m/z): 648 (M+, 100). 1H NMR
(CDCl3, 200 MHz) δ: 7.84-7.88 (4H, d, J ) 7.9 Hz, Ar-H),
7.62-7.67 (2H, q, J ) 1.6, 9.9 Hz, Ar-H), 7.35-7.43 (2H, t, J
) 7.3 Hz, Ar-H), 7.08-7.16 (2H, t, J ) 7.6 Hz, Ar-H), 6.98
(2H, s, Th-H), 6.95-6.98 (2H, m, Ar-H), 6.73-6.80 (2H, d, J )
7.6 Hz, Ar-H), 6.77 (2H, s, Th-H), 2.46-2.54 (4H, t, J ) 7.3
Hz, CH2), 1.61-1.71 (4H, m, CH2), 1.27-1.43 (12H, m, CH2),
0.83-0.89 (6H, t, J ) 6.3 Hz, CH3). 13C NMR (CDCl3, 50 MHz)
δ: 149.16, 148.92, 144.20, 141.23, 141.08, 134.40, 127.88,
127.80, 127.74, 125.73, 124.63, 124.07, 121.17, 120.39, 119.99,
119.33, 31.62, 30.57, 30.40, 28.97, 22.58, 14.08. FT-IR (λ, cm-1):
3094, 2960, 2925, 1465, 823, 770, 754, 729, 641. Anal. Calcd
for C45H44S2: C, 83.29; H, 6.83; S, 9.88. Found: C, 82.97; H,
6.69; S, 10.01.
2,7-Bis(3,4′-d ih exyl-5,2′-bith iop h en e-2-yl)-9,9′-sp ir obi-
flu oen e (6b). Brown solids (yield 99%). EI-MS (m/z): 980 (M+,
100). 1H NMR (CDCl3, 300 MHz) δ: 7.90-7.92 (2H, d, J ) 8.0
Hz, Ar-H), 7.80-7.83 (2H, d, J ) 8.0 Hz, Ar-H), 7.60-7.62 (2H,
dd, J ) 1.6, 8.0 Hz, Ar-H), 7.39-7.44 (2H, t, J ) 7.2 Hz, Ar-
H), 7.12-7.17 (2H, t, J ) 7.2 Hz, Ar-H), 6.94 (2H, s, Th-H),
6.90-6.91 (4H, m, Ar-H, Th-H), 6.81-6.85 (4H, m, Ar-H, Th-
H), 2.63-2.69 (4H, t, J ) 8.0 Hz, CH2), 2.55-2.60 (4H, t, J )
8.0 Hz, CH2), 1.53-1.59 (8H, m, CH2), 1.27-1.32 (24H, m,
CH2), 0.84-0.89 (12H, m, CH3). 13C NMR (CDCl3, 75.5 MHz)
δ: 149.8, 148.3, 143.5, 141.7, 141.3, 140.6, 140.1, 135.7, 133.8,
130.5, 128.0, 127.8, 126.9, 126.0, 125.4, 124.2, 120.7, 120.3,
120.0, 119.7, 31.6, 31.5, 30.5, 30.4, 30.3, 29.3, 29.1, 28.9, 22.5,
14.0, 13.9. FT-IR (λ, cm-1): 3062, 2953, 1447, 816, 757, 735,
639. Anal. Calcd for C65H72S4: C, 79.54; H, 7.39; S, 13.07.
Found: C, 79.48; H, 7.52; S, 13.35.
2,2′-Bis(3,4′-d ih exyl-5,2′-bith iop h en e-2-yl)-9,9′-sp ir obi-
flu oen e (6c). Brown solids (yield 97%). EI-MS (m/z): 980 (M+,
100). 1H NMR (CDCl3, 300 MHz) δ: 7.84-7.86 (4H, d, J ) 7.6
Hz, Ar-H), 7.61-7.64 (2H, dd, J ) 1.6, 8.0 Hz, Ar-H), 7.35-
7.40 (2H, td, J ) 1.0, 7.6 Hz, Ar-H), 7.08-7.13 (2H, td, J )
1.0, 7.4 Hz, Ar-H), 6.96 (4H, s, Th-H), 6.88-6.89 (2H, d, J )
1.2 Hz, Ar-H), 6.83 (2H, s, Th-H), 6.72-6.75 (2H, J ) 7.2 Hz,
Ar-H), 2.62-2.67 (4H, t, J ) 7.8 Hz, CH2), 2.53-2.58 (4H, t, J
) 7.6 Hz, CH2), 1.53-1.58 (8H, m, CH2), 1.24-1.31 (24H, m,
CH2), 0.82-0.90 (12H, m, CH3). 13C NMR (CDCl3, 75.5 MHz)
δ: 149.2, 148.9, 143.5, 141.3, 141.2, 141.1, 140.1, 135.7, 133.8,
130.4, 127.9, 127.8, 126.9, 126.1, 125.5, 124.0, 120.9, 120.4,
119.9, 119.7, 31.6, 31.5, 30.5, 30.4, 30.3, 29.3, 29.1, 28.9, 22.5,
14.0, 13.9. FT-IR (λ, cm-1): 3068, 2924, 1458, 1443, 1415, 851,
825, 754, 729. Anal. Calcd for C65H72S4: C, 79.54; H, 7.39; S,
13.07. Found: C, 79.42; H, 7.71; S, 12.89.
2,7-Bis(3,4′,4′′-tr ih exyl-5,2′:5′,2′′-ter th iop h en e-2-yl)-9,9′-
sp ir obiflu oen e (7b). Brown solids (yield 97%). EI-MS (m/z):
1313 (M+, 100). 1H NMR (CDCl3, 300 MHz) δ: 7.92-7.94 (2H,
d, J ) 7.6 Hz, Ar-H), 7.81-7.84 (2H, d, J ) 8.0 Hz, Ar-H),
7.61-7.64 (2H, dd, J ) 1.6, 8.0 Hz, Ar-H), 7.41-7.46 (2H, t, J
) 7.2 Hz, Ar-H), 7.14-7.19 (2H, t, J ) 7.4 Hz, Ar-H), 6.98
(2H, s, Th-H), 6.96-6.97 (2H, d, J ) 1.6 Hz, Ar-H), 6.92 (4H,
s, Th-H), 6.89 (2H, s, Th-H), 6.83-6.86 (2H, d, J ) 7.6 Hz,
Ar-H), 2.67-2.76 (8H, m, Ar-H), 2.59-2.64 (4H, t, J ) 7.8 Hz,
CH2), 1.57-1.70 (12H, m, CH2), 1.24-1.34 (36H, m, CH2),
0.87-0.96 (18H, m, CH3). 13C NMR (CDCl3, 75.5 MHz) δ:
149.8, 148.3, 143.5, 141.7, 141.4, 140.6, 140.3, 139.4, 133.7,
133.6, 130.7, 130.1, 128.2, 128.0, 127.8, 127.0, 126.2, 125.5,
124.9, 124.2, 120.7, 120.3, 120.0, 119.9, 119.7, 31.6, 31.5, 31.4,
30.5, 30.4, 30.3, 30.2, 29.5, 29.2, 29.1, 28.9, 22.5, 20.9, 14.1,
13.9. FT-IR (λ, cm-1): 3057, 2954, 1475, 1446, 1420, 1375, 816,
757, 735, 639. Anal. Calcd for C85H100S6: C, 77.69; H, 7.67; S,
14.64. Found: C, 77.76; H, 8.02; S, 14.33.
2-(5′-Br om o-3,4′-dih exyl-5,2′-bith ioph en e-2-yl)-9,9′-spir o-
biflu oen e (13). Yellow crystals (yield 94%). EI-MS (m/z): 728,
1
726 (M+, 100). H NMR (CDCl3, 300 MHz) δ: 7.82-7.90 (4H,
m, Ar-H), 7.59-7.62 (1H, dd, J ) 1.6, 8.0 Hz, Ar-H), 7.34-
7.42 (3H, m, Ar-H), 7.08-7.15 (3H, m, Ar-H), 6.95 (1H, s, Th-
H), 6.92-6.93 (1H, d, J ) 0.8 Hz, Ar-H), 6.77-6.79 (2H, d, J
) 7.6 Hz, Ar-H), 6.76 (1H, s, Th-H), 6.70-6.72 (1H, d, J ) 7.2
Hz, Ar-H), 2.59-2.64 (2H, t, J ) 7.8 Hz, CH2), 2.51-2.56 (2H,
t, J ) 7.6 Hz, CH2), 1.53-1.58 (4H, m, CH2), 1.22-1.37 (12H,
m, CH2), 0.84-0.92 (6H, m, CH3). 13C NMR (CDCl3, 75.5 MHz)
δ: 149.4, 149.1, 148.4, 142.3, 141.9, 141.7, 141.4, 141.0, 140.6,
135.6, 133.5, 129.3, 127.8, 127.7, 126.4, 126.0, 125.4, 124.1,
123.9, 120.9, 120.3, 120.0, 119.9, 108.3, 31.5, 30.5, 29.5, 29.4,
29.3, 29.1, 28.8, 22.5, 14.0, 13.9. FT-IR (λ, cm-1): 3057, 2957,
1459, 1446, 825, 753, 734, 637. Anal. Calcd for C45H43BrS2:
C, 74.26; H, 5.95; Br, 10.98; S, 8.81. Found: C, 74.07; H, 5.87;
Br, 11.32; S, 8.73.
Gen er a l p r oced u r e for p r ep a r a tion of 2,7-Bis(4-h exy-
lth ien yl)-9,9′-sp ir obiflu or en e (5b), 2,2′-Bis(4-h exylth ie-
n yl)-9,9′-sp ir ob iflu or en e (5c), 2,7-Bis(3,4′-d ih exyl-5,2′-
bith iop h en e-2-yl)-9,9′-sp ir obiflu oen e (6b), 2,2′-Bis(3,4′-
dih exyl-5,2′-bith ioph en e-2-yl)-9,9′-spir obiflu oen e (6c), 2,7-
Bis(3,4′,4′′-t r ih e xyl-5,2′:5′,2′′-t e r t h iop h e n e -2-yl)-9,9′-
sp ir obiflu oen e (7b), a n d 2,2-Bis(3,4′,4′′-tr ih exyl-5,2′:5′,2′′-
ter th ioph en e-2-yl)-9,9′-spir obiflu oen e (7c).Thesecompounds
were prepared according to the procedure described for
compounds 5-7a and Pd(PPh3)4 (70 mg, 0.06 mmol), compound
1b, 1c, 10, 11, 14, or 15 (2 mmol) in THF, compound 8 (2.0 g,
8 mmol) and NaHCO3 (20 mL). Pure products were obtained
through flash chromatography (silica gel, CHCl3/hexane 1:25).
2,7-Bis(4-h exylth ien yl)-9,9′-sp ir obiflu or en e (5b). Yellow
crystals (yield 98%). EI-MS (m/e): 648 (M+, 100). 1H NMR
(CDCl3, 300 MHz) δ: 7.89-7.91 (2H, d, J ) 7.6 Hz, Ar-H),
7.80-7.82 (2H, d, J ) 8.0 Hz, Ar-H), 7.62-7.65 (2H, dd, J )
1.6, 8.0 Hz, Ar-H), 7.37-7.42 (2H, td, J ) 1.1, 7.4 Hz, Ar-H),
7.11-7.17 (2H, td, J ) 1.1 , 7.4 Hz, Ar-H), 6.95-6.96 (2H, d,
J ) 1.2 Hz, Th-H), 6.90-6.91 (2H, d, J ) 0.8 Hz, Ar-H), 6.80-
6.83 (2H, dd, J ) 0.8, 7.6 Hz, Ar-H), 6.76 (2H, s, Th-H), 2.48-
2.53 (4H, t, J ) 7.6 Hz, CH2), 1.53-1.58 (4H, m, CH2), 1.23-
1.32 (12H, m, CH2), 0.85-0.89 (6H, t, J ) 6.6 Hz, CH3). 13C
NMR (CDCl3, 75.5 MHz) δ: 149.7, 148.4, 144.1, 143.7, 141.7,
140.5, 134.2, 127.9, 127.7, 125.7, 124.5, 124.2, 120.9, 120.2,
120.0, 119.3, 31.5, 30.5, 30.3, 28.9, 22.5, 14.0. FT-IR (λ, cm-1):
3057, 2953, 1475, 867, 816, 755, 732, 638. Anal. Calcd for
2,2′-Bis(3,4′,4′′-tr ih exyl-5,2′:5′,2′′-ter th iop h en e-2-yl)-9,9′-
sp ir obiflu oen e (7c). Brown solids (yield: 97%). EI-MS (m/
1
z): 1313 (M+, 100). H NMR (CDCl3, 300 MHz) δ: 7.88-7.91
(4H, d, J ) 7.6 Hz, Ar-H), 7.67-7.70 (2H, dd, J ) 1.4, 7.8 Hz,
Ar-H), 7.39-7.44 (2H, t, J ) 7.4 Hz, Ar-H), 7.13-7.18 (2H, t,
J ) 7.4 Hz, Ar-H), 7.03-7.06 (4H, m, Th-H), 7.00-7.01 (2H,
d, J ) 1.2 Hz, Ar-H), 6.95-6.97 (2H, m, Th-H), 6.91 (2H, s,
Th-H), 6.76-6.81 (2H, d, J ) 7.2 Hz, Ar-H), 2.61-2.80 (12H,
C
45H44S2: C, 83.29; H, 6.83; S, 9.88. Found: C, 82.99; H, 6.71;
S, 9.60.
4934 J . Org. Chem., Vol. 67, No. 14, 2002