M. Sonntag, P. Strohriegl / Tetrahedron 62 (2006) 8103–8108
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slowly. The reaction mixture was stirred at 0 ꢀC for 1 h and
15 ml of an aqueous NH4Cl solution was added. Thereafter,
the reaction batch was poured into 150 ml water and ex-
tracted with diethyl ether. The organic layer was washed
with water and the solvent was removed. The product was
purified by column chromatography on silica gel with hex-
ane/ethyl acetate (1.5:1) as eluent yielding 0.35 g (95%) of
4a as a colorless solid. 1H NMR (250 MHz, DMSO):
d (ppm) 0.74 (t, 3H), 1.29–1.33 (m, 6H), 1.67 (m, 3H),
2.01 (m, 1H), 2.24 (m, 1H), 4.93 (m, 3H), 5.14 (m, 2H),
7.20 (d, 2H), 7.35–7.51 (m, 6H), 7.68 (d, 2H), 7.73 (d,
2H), 8.29 (d, 2H). MS (70 eV): m/z¼463 (M+).
4.13 (q, 2H), 4.51 (s, 3H), 7.32–7.40 (m, 4H), 7.55 (d,
2H), 7.72 (s, 2H), 7.86 (d, 2H), 8.20 (s, 2H). MS (70 eV):
m/z¼385 (M+).
4.11.1,10-Di-n-butyl-1,10-dimethyl-bisindeno[3,2-b:2030-h]-
9-sec-butyl-carbazole (7)
Compound 5a (60 mg, 0.14 mmol) was dissolved in 15 ml
THF (abs) under argon. The solution was cooled to
ꢁ78 ꢀC before 0.19 ml (0.3 mmol) n-BuLi (1.6 M solution
in hexane) was added slowly. After 15 min stirring, 0.2 ml
(0.4 mmol) 1-bromobutane was added. The solution was al-
lowed to warm to room temperature and stirred for another
hour before it was poured into 50 ml ice water. The reaction
batch was extracted with diethyl ether, the organic phase was
washed with water, and the solvent was evaporated. Purifica-
tion was carried out by column chromatography on silica gel
with hexane/THF (10:1) as eluent. In addition, 7 was purified
by MPLC with hexane/THF (15:1) at a pressure of 18 bar.
4.6. 2,7-Bis-[2-(2-hydroxyethylphenyl)-9-
(2-ethylhexyl)]-carbazole (4b)
Compound 4b was prepared according to the procedure de-
scribed above (yield: 96%). H NMR (250 MHz, CDCl3):
1
d (ppm) 0.71–0.88 (m, 6H), 1.14–1.46 (m, 11H), 1.49 (d,
3H), 2.07 (m, 1H), 4.16 (d, 2H), 5.09 (m, 2H), 7.17 (d,
2H), 7.36–7.49 (m, 8H), 7.71 (d, 2H), 8.12 (d, 2H). MS
(70 eV): m/z¼519 (M+).
1
The reaction yielded 51 mg (75%) of 7 as white solid. H
NMR (250 MHz, CDCl3): d (ppm) 0.62 (m, 9H), 0.87 (t,
4H), 1.01–1.10 (m, 4H), 1.51 (m, 6H), 1.74 (d, 3H), 1.96–
2.17 (m, 5H), 2.28–2.47 (m, 1H), 4.76 (m, 1H), 7.27–7.37
(m, 6H), 7.69 (s, 2H), 7.76 (d, 2H), 8.01 (s, 2H). 13C NMR
(62.5 MHz, CDCl3): d (ppm) 12.2, 14.3, 19.6, 23.5, 26.9,
28.1, 28.6, 41.8, 50.4, 53.6, 114.1, 119.9, 123.2, 123.3,
123.6, 127.1, 127.3, 128.5, 141.2, 143.7, 153.4. IR (Si-
wafer): ~n (cmꢁ1) 3011, 2958, 2972, 1488, 1452, 1378,
1342, 1240, 740. MS (70 eV): m/z¼539 (M+). Anal. Calcd
for C40H45N (539.8): C, 89.00; H, 8.40; N, 2.59. Found: C,
89.09; H, 8.31; N, 2.58.
4.7. 2,7-Bis-[2-(2-hydroxyethylphenyl)-9-methyl]-
carbazole (4c)
Compound 4c was prepared according to the procedure de-
scribed above (yield: 98%). H NMR (250 MHz, CDCl3):
1
d (ppm) 1.45 (d, 6H), 3.90 (s, 3H), 5.10 (q, 2H), 7.18 (d,
1H), 7.35–7.40 (m, 6H), 7.43–7.51 (m, 3H), 7.73 (d, 2H),
8.15 (d, 2H). MS (70 eV): m/z¼421 (M+).
4.8. 1,10-Dimethyl-bisindeno[3,2-b:2030-h]-9-sec-butyl-
carbazole (5a)
4.12. 1,1-Dimethyl-10,10-dimethyl-bisindeno[3,2-b:2030-h]-
9-sec-butyl-carbazole (6)
To a solution of 0.1 g (0.22 mmol) 4a in 10 ml dichloro-
methane, 0.1 ml (0.65 mmol) boron trifluoride etherate was
added. The mixture was stirred for 30 min at room tempera-
ture before 15 ml ethanol and 20 ml water were added. The
reaction batch was extracted with dichloromethane, washed
with water, and dried with Na2SO4 before the solvent was
evaporated. Purification by column chromatography on
silica gel with hexane/THF (3:1) as eluent yielded 83 mg
(92%) of 5a as colorless solid. 1H NMR (250 MHz,
DMSO): d (ppm) 0.81 (t, 3H), 1.64 (d, 6H), 1.80 (d, 3H),
2.12 (m, 1H), 2.49 (m, 1H), 4.10 (q, 2H), 5.05 (m, 1H),
7.35–7.46 (m, 4H), 7.64 (d, 2H), 8.12 (d, 2H), 8.21 (s,
2H), 8.39 (d, 2H). MS (70 eV): m/z¼427 (M+).
Compound 6 was prepared according to the procedure de-
scribed for 7. For alkylation, iodomethane was used (yield:
70%). Compound 6 was purified by MPLC with hexane/
1
THF (10:1) at a pressure of 18 bar. H NMR (250 MHz,
CDCl3): d (ppm) 0.90 (t, 3H), 1.61 (m, 12H), 1.78 (d, 3H),
2.05–2.21 (m, 1H), 2.35–2.53 (m, 1H), 4.81 (m, 1H),
7.28–7.49 (m, 6H), 7.82 (s, 2H), 7.89 (d, 2H), 8.15 (s, 2H).
13C NMR (62.5 MHz, CDCl3): d (ppm) 12.2, 19.6, 26.8,
28.5, 46.5, 53.6, 101.4, 114.0, 120.8, 123.1, 123.7, 127.4,
132.1, 137.6, 140.3, 145.3, 154.9. IR (Si-wafer): ~n (cmꢁ1
)
3014, 2961, 2926, 1489, 1452, 1377, 1342, 1241, 740. MS
(70 eV): m/z¼455 (M+). Anal. Calcd for C34H33N (455.7):
C, 89.63; H, 7.30; N, 3.07. Found: C, 89.56; H, 7.33; N, 3.12.
4.9. 1,10-Dimethyl-bisindeno[3,2-b:2030-h]-9-(2-ethyl-
hexyl)-carbazole (5b)
4.13. 1,10-Diethyl-1,10-dimethyl-bisindeno[3,2-b:2030-h]-
9-sec-butyl-carbazole (8)
Compound 5b was prepared as described above (yield: 90%).
1H NMR (250 MHz, CDCl3): d (ppm) 0.84 (m, 6H), 1.51–
1.46 (m, 8H), 1.49 (d, 6H), 2.05 (m, 1H), 3.96 (q, 2H),
4.86 (m, 2H), 7.33–7.44 (m, 4H), 7.60 (d, 2H), 8.10 (d,
2H), 8.19 (s, 2H), 8.35 (d, 2H). MS (70 eV): m/z¼483 (M+).
4.10. 1,10-Dimethyl-bisindeno[3,2-b:2030-h]-9-methyl-
carbazole (5c)
Compound 8 was prepared according to the procedure de-
scribed for 7. For alkylation, bromoethane was used. Com-
pound 8 was purified by MPLC with hexane/THF (15:1) at
a pressure of 18 bar (yield: 80%). 1H NMR (250 MHz,
CDCl3): d (ppm) 0.41 (m, 6H), 0.90 (m, 3H), 1.58 (s, 6H),
1.78 (d, 3H), 2.05–2.22 (m, 5H), 2.34–2.41 (m, 1H), 4.78
(m, 1H), 7.26–7.41 (m, 6H), 7.78 (s, 2H), 7.82 (d, 2H),
8.05 (s, 2H). 13C NMR (62.5 MHz, CDCl3): d (ppm) 9.0,
11.8, 19.2, 27.3, 28.2, 34.1, 50.4, 53.2, 113.7, 115.0,
119.4, 122.9, 124.1, 126.4, 138.3, 141.0, 142.9, 152.6. IR
(Si-wafer): ~n (cmꢁ1) 3049, 2963, 2929, 1488, 1452, 1378,
Compound 5c was prepared as described above (yield:
88%). H NMR (250 MHz, CDCl3): d (ppm) 1.56 (d, 6H),
1