2472
F. Dierschke et al.
SHORT PAPER
ther purified by recrystallisation from EtOH to give the title
compound as a yellow solid (0.9 g, 58%); mp 188–191 °C.
1H NMR (250 MHz, CDCl3): = 8.72 (s, 2 H), 7.71 (s, 2 H), 4.17
(m, 2 H, NCH2), 1.99 (m, 1 H, CH), 1.30 (br m, 8 H, alkyl), 0.93 (m,
6 H, 2 CH3).
13C NMR (75.46 MHz, CDCl3): = 143.72, 143.14, 120.92, 119.49,
115.92, 113.84, 48.45, 39.28, 30.65, 28.42, 24.26, 22.91, 13.95,
10.79.
4 h at 50 °C and then quenched with ice. The inorganic precipitate
was dissolved in 2 M HCl (2 M) and the product was extracted with
CH2Cl2. The organic fractions were dried (MgSO4) and the solvent
was removed under reduced pressure. The product was purified by
column chromatography (10% EtOAc in hexane) to provide 9 as a
yellowish solid (1.6 g, 75%); mp 90–93 °C.
1H NMR (250 MHz, CD2Cl2): = 8.00 (s, 2 H), 7.75 (d, J = 7.58
Hz, 6 H), 7.29 (d, J = 8.21 Hz, 4 H), 4.23 (m, 2 H, NCH2), 2.68 (t,
J = 7.7 Hz, 4 H, ArCH2), 2.13 (m, 1 H, CH), 1.66–1.27(br m, 42 H,
alkyl), 0.92 (m, 12 H, 4 CH3).
MS: m/z = 526.2 [M+] (calcd 527.22).
13C NMR (75.47 MHz, CD2Cl2): = 196.05, 150.26, 143.51,
135.61, 132.95, 131.18, 129.40, 122.57, 121.77, 118.60, 115.18,
48.86, 40.05, 36.84, 32.72, 31.92, 31.51, 30.41, 30.37, 30.25, 30.13,
29.36, 25.14, 23.85, 23.49, 14.71, 14.62, 11.49.
Anal. Calcd for C20H21Br2N3O4: C, 45.56; H, 4.01; N, 7.97. Found:
C, 45.66; H, 3.96; N, 7.89.
3,6-Dibenzoyl-2,7-dibromo-N-(2-ethylhexyl)carbazole (8)
To a mixture of compound 6 (1 g, 2.28 mmol) and AlCl3 (3.4 g, 25.5
mmol) in nitrobenzene (14 mL) was added benzoic anhydride (1.54
g, 6.8 mmol) at 0 °C. The reaction mixture was stirred for 8 h and
then quenched with ice. The inorganic precipitate was dissolved in
2 M HCl and the product was extracted with Et2O (3 × 50 mL). The
combined organic fractions were dried (MgSO4) and the solvent
was removed under reduced pressure. The product was first purified
by column chromatography (20% EtOAc in hexane) and then re-
crystallisation from EtOAc to afford the title compound as a white
solid (1.1 g, 76%); mp 201–203 °C.
MS: m/z = 925.00 [M+] (calcd 925.98).
Anal. Calcd for C54H71Br2NO2: C, 70.04; H, 7.73; N, 1.51. Found:
C, 69.96; H, 7.71; N, 1.45.
Acknowledgement
This research was supported by the BMBF through projects OLED
and OLAS.
1H NMR (250 MHz, CDCl3): = 7.99 (s, 2 H), 7.83 (d, J = 7.26 Hz,
4 H), 7.67 (s, 2 H), 7.57 (m, 2 H), 7.54 (t, J = 7.26 Hz, 4 H), 4.15
(m, 2 H, NCH2), 2.06 (m, 1 H, CH), 1.35 (br m, 8 H, alkyl), 0.92 (m,
6 H, 2 CH3).
13C NMR (62.89 MHz, CDCl3): = 195.92, 142.77, 137.12, 133.38,
131.94, 130.34, 128.52, 122.14, 120.95, 118.18, 114.38, 48.05,
39.26, 30.75, 28.53, 24.33, 23.00, 13.99, 10.88.
References
(1) Kraft, A.; Grimsdale, A. C.; Holmes, A. B. Angew. Chem.
Int. Ed. 1998, 37, 402.
(2) Brabec, C. J.; Sariciftici, N. S.; Hummelen, J. C. Adv. Funct.
Mater. 2001, 11, 15.
(3) Dimitrakopoulos, C. D.; Malefant, P. R. Adv. Mater. 2001,
14, 99.
MS: m/z = 645.1 [M+] (calcd 645.44).
(4) (a) Morin, J.-F.; Leclerc, M. Macromolecules 2001, 34,
4680. (b) Zotti, G.; Schiavon, G.; Zecchin, S.; Morin, J.-F.;
Leclerc, M. Macromolecules 2002, 35, 2122.
(5) Yamato, T.; Hideshima, C.; Suehiro, K.; Tashiro, M.;
Prakash, G. K. S.; Olah, G. A. J. Org. Chem. 1991, 56, 6248.
(6) Shaw, R. S.; Turner, E. E. J. Chem. Soc. 1932, 285.
(7) Cadogan, J. I. G.; Cameron-Wood, M.; Makie, R. K.; Searle,
R. J. G. J. Chem. Soc. 1965, 4831.
Anal. Calcd for C34H31Br2NO2: C, 63.27; H, 4.89; N, 2.17. Found:
C, 63.28; H, 4.73; N, 2.19.
2,7-Dibromo-N-(2-ethylhexyl)-3,6-bis(4-octylbenzoyl)carba-
zole (9)
To a mixture of compound 6 (1 g, 2.28 mmol) and AlCl3 (0.73 g, 5.5
mmol) in 1,2-dichloroethane (3 mL) was added slowly, 4-octylben-
zoyl chloride (1.35 g, 4.8 mmol) at r.t. The mixture was stirred for
Synthesis 2003, No. 16, 2470–2472 © Thieme Stuttgart · New York