2-(4-tert-Butylphenyl)-5-{4-[9,9-dihexyl-2-
solution which was heated at 80 uC with stirring for 16 h. After
cooling to room temperature water was added and the layers
separated. The aqueous layer was extracted with diethyl ether
and the combined organic extracts were washed with brine,
dried over MgSO4, filtered and concentrated to yield yellow
oil. The product was purified by column chromatography on
silica eluting with DCM to yield 14 as a yellow solid which was
dried under vacuum mp: .400 uC; Tg 76 uC (306 mg, 90%).
Anal. calcd for C55H59N3O: C, 84.90; H, 7.64; N, 5.40. Found:
C, 84.68; H, 7.66; N, 5.12%; 1H NMR (CDCl3): d 0.71 (s, 4H),
0.80 (t, J = 7.2, 6H), 1.07 (m, 12H), 1.39 (s, 9H), 1.90 (m, 4H),
7.03 (m, 3H), 7.14 (m, 4H), 7.24 (m, 5H), 7.58 (m, 5H), 7.70 (d,
J = 8.0, 1H), 7.83 (d, J = 8.8, 2H), 8.10 (d, J = 8.4, 2H), 8.23 (d,
J = 8.8, 2H) ppm; 13C NMR (CDCl3): d 14.01, 22.54, 23.82,
29.62, 31.15, 31.51, 35.11, 40.26, 55.25, 119.27, 119.53, 120.62,
121.24, 122.47, 122.60, 123.52, 123.92, 126.07, 126.12, 126.82,
127.35, 127.60, 127.70, 129.19, 135.58, 137.79, 141.24, 144.91,
147.49, 147.98, 151.60, 152.51, 155.34, 164.40, 164.67 ppm; MS
(ES+): m/z 778.7 (M+).
(trimethylsilyl)fluoren-7-yl]phenyl}-1,3,4-oxadiazole (12)
A mixture of 10 (3.00 g, 5.6 mmol), 11 (2.01 g, 5.6 mmol)
(synthesised as described in the ESI{), potassium carbonate
(1 M solution, 30 cm3) and THF (50 cm3) was degassed for
1 h before tetrakis-(triphenylphosphine)palladium (330 mg,
5 mol %) was added and the mixture was refluxed under argon
at 80 uC for 65 h. After cooling to room temperature, the
layers were separated and the aqueous layer was extracted with
ethyl acetate. The combined organic extracts were washed with
brine, dried over MgSO4, filtered and concentrated to yield a
dark oil. This was purified by column chromatography on
silica eluting with DCM. The product was recrystallised from
ethanol to yield 12 as a white crystalline solid (3.00 g, 78%),
mp: 144.0–144.7 uC. Anal. calcd for C46H58N2OSi: C, 80.89;
H, 8.56; N, 4.10. Found: C, 81.11; H, 8.57; N, 4.10%; 1H NMR
(CDCl3): d 0.34 (s, 9H), 0.75 (m, 4H), 0.78 (t, J = 6.4 Hz, 6H),
1.09 (m, 12H), 1.40 (s, 9H), 2.03 (m, 4H), 7.52 (m, 2H), 7.58 (d,
J = 8.8 Hz, 2H), 7.63 (m, 2H), 7.73 (d, J = 7.6 Hz, 1H), 7.81 (d,
J = 8.0 Hz, 1H), 7.84 (d, J = 8.4 Hz, 2H), 8.11 (d, J = 8.4 Hz,
2H), 8.24 (d, J = 8.4 Hz, 2H) ppm; 13C NMR (CDCl3): d 0.00,
14.85, 23.35, 24.59, 30.44, 32.03, 32.23, 36.00, 41.02, 56.07,
120.07, 121.11, 122.09, 122.39, 123.46, 126.96, 127.71, 128.24,
128.53, 128.58, 132.79, 139.59, 140.40, 141.95, 142.25, 145.81,
151.11, 152.76, 156.24, 165.27, 165.57 ppm; MS (EI): m/z
682 (M+).
7-{4-[5-(4-tert-Butylphenyl)-1,3,4-oxadiazol-2-yl]phenyl}-9,9-
dihexyl-N-phenylfluoren-2-amine (15)
A mixture of 13 (500 mg, 0.72 mmol), aniline (0.13 cm3,
1.4 mmol), sodium tert-butoxide (80 mg, 0.83 mmol),
tris(dibenzylideneacetone)dipalladium (35 mg 5 mol %), tri-
tert-butylphosphine (y15 mg) and dry toluene (30 cm3) was
heated at 80 uC for 16 h. Workup as described for 14 yielded a
brown oil which was purified by column chromatography on
silica eluting with DCM. The product was recrystallised from
ethanol to yield 15 as a yellow crystalline solid (0.41 g, 81%),
mp: 169.2–170.2 uC. Anal. calcd for C49H55N3O: C, 83.84; H,
2-(4-tert-Butylphenyl)-5-[4-(9,9-dihexyl-2-bromofluoren-7-
yl)phenyl]-1,3,4-oxadiazole (13)
A mixture of 12 (3.00 g, 4.4 mmol), sodium acetate (0.75 g,
9.0 mmol) and dry THF (40 cm3) was cooled in the dark to 0 uC
in an ice bath. Bromine (0.90 g, 17.5 mmol) was added and the
solution was stirred for 2 h with the ice bath removed. The
reaction was then quenched with triethylamine (4.9 cm3,
8 equiv.) producing a white precipitate. A saturated sodium
thiosulfate solution was then added to quench the excess
bromine. The product was extracted with diethyl ether and
the combined organic extracts were washed with water, dried
over MgSO4, filtered and concentrated. The resulting solid
was recrystallised from ethanol to yield 13 as shiny white
crystals (2.82 g, 93%), mp: 133.9–134.8 uC. Anal. calcd for
C43H49BrN2O: C, 74.87; H, 7.16; N, 3.97. Found: C, 75.23; H,
1
7.90; N, 5.99. Found: C, 83.79; H, 7.90; N, 5.79%; H NMR
(CDCl3): d 0.70 (m, 10H), 1.05 (m, 12H), 1.36 (s, 9H), 2.00 (m,
4H), 6.86 (t, J = 7.1, 1H), 7.12 (m, 4H), 7.26 (t, J = 8.2, 2H),
7.68 (d, J = 8.2, 2H), 7.73 (m, 2H), 7.80 (2H), 8.01 (d, J = 8.2,
2H), 8.10 (d, J = 8.2, 2H), 8.22 (d, J = 8.2, 2H), 8.38 (s, 1H)
ppm; 13C NMR (CDCl3): d 13.74, 21.88, 23.43, 28.88, 30.81,
30.86, 34.83, 38.30, 54.64, 111.88, 116.61, 117.33, 119.85,
120.41, 121.38, 121.53, 121.77, 122.42, 126.51, 126.98, 127.29,
127.90, 128.03, 129.90, 132.87, 136.64, 142.11, 143.89, 144.15,
144.54, 151.28, 152.75, 155.71, 164.51, 164.72 ppm.
7-{4-[5-(4-tert-Butylphenyl)-1,3,4-oxadiazol-2-yl]phenyl}-N-{2-
[4-(5-(4-tert-butylphenyl)-1,3,4-oxadiazol-2-yl)phenyl]-9,9-
dihexyl-fluoren-7-yl}-9,9-dihexyl-N-phenyl-9H-fluoren-2-amine
(16)
1
7.23; N, 3.97%; H NMR (CDCl3): d 0.74 (m, 10H), 1.04 (m,
12H), 1.37, (s, 9H), 2.00 (m, 4H), 7.49 (m, 2H), 7.59 (m, 5H),
7.82 (m, 3H), 8.08 (d, J = 7.9, 2H), 8.22 (d, J = 7.9, 2H) ppm;
13C NMR (CDCl3): d 13.96, 22.54, 23.73, 29.61, 31.14, 31.44,
35.11, 40.28, 55.61, 120.24, 121.18, 121.26, 121.40, 121.45,
122.76, 126.08, 126.27, 126.31, 126.82, 127.38, 127.72, 130.11,
139.12, 139.52, 140.26, 144.65, 151.30, 153.30, 155.40, 164.32,
164.73 ppm.
A mixture of 15 (360 mg, 0.51 mmol), 13 (0.360 mg,
0.52 mmol), sodium tert-butoxide (80 mg, 0.83 mmol),
tris(dibenzylideneacetone)dipalladium (25 mg, 5 mol %), tri-
tert-butylphosphine (y15 mg) and dry toluene (30 cm3) was
heated at 80 uC for 16 h. Workup as described for 14 yielded a
brown oil which was purified by column chromatography on
silica (eluent DCM–ethyl acetate 9 : 1 v/v). The product was
recrystallised from ethanol to yield 16 as a yellow solid (0.48 g,
71%) mp: .400 uC; Tg 146 uC. Anal. calcd for C92H103N5O2:
C, 84.30; H, 7.92; N, 5.34. Found: C, 84.10; H, 7.94; N, 5.35%;
1H NMR (CDCl3): d 0.77 (m, 20H), 1.70, (m, 24H), 1.39 (s,
18H), 1.95 (m, 8H), 7.07 (m, 3H), 7.20 (m, 4H), 7.28 (m, 2H),
7-{4-[5-(4-tert-Butylphenyl)-1,3,4-oxadiazol-2-yl]phenyl}-9,9-
dihexyl-N,N-diphenylfluoren-2-amine (14)
A mixture of 13 (300 mg, 0.4 mmol), diphenylamine (74 mg,
0.4 mmol), sodium tert-butoxide (58 mg, 0.6 mmol), tris(di-
benzylideneacetone)dipalladium (5 mg), tri-tert-butylphos-
phine (y2 mg) and dry toluene (25 cm3) gave a dark red
This journal is ß The Royal Society of Chemistry 2006
J. Mater. Chem., 2006, 16, 3823–3835 | 3833